Heterocyclic aromatic anion salts, and their uses as ionic conducting materials

ABSTRACT

The invention relates to ionic compounds in which the anionic load has been displaced, and the uses of these compounds. A compound disclosed by the invention comprises an anionic portion combined with at least one cationic portion M +m  in sufficient numbers to ensure overall electronic neutrality. The anionic portion is comprised of one of the groups (A) and (B):                    
     wherein Y 1 , Y 2 , Y 3 , Y 4  and Y 5  represent a carbonyl group, a sulfonyl group, a thiocarbonyl group, a thionyl group, a —C(═NCN)— or a —C(═C(CN) 2 )— group; Z represents an electroattractive radical; each of the substituents, R A , R B , R C  and R D  represents independently of one another a monovalent or divalent organic radical or is part of a polymer chain, with at least one of the substituents R C  and R D  being a perfluorinated radical. The compounds can be used especially for ionic conducting materials, electronic conducting materials, colorants, and the catalysis of various chemical reactions.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.09/101,811 filed on Nov. 19, 1998 now U.S. Pat. No. 6,171,522, which isbased on PCT Patent application No. PCT/CA97/01011 filed on Dec. 30,1997, which is based on Canadian Patent Application No. 2,194,127 filedon Dec. 30, 1996 and on Canadian Patent Application No. 2,199,231 filedon Mar. 5, 1997.

It is an object of the present invention to provide ionic compounds inwhich the anionic charge is delocalized, and their uses.

Derivatives of non-nucleophilic or slightly basic anions have anincreasing importance in all applications of chemistry to stabilize oractivate various cationic charges such as those of colouring materialsor intermediate species in polymerizations. They also act asintermediates for various reactions of organic chemistry. Inelectrochemistry, media other than water are more and more relied uponfor applications such as primary or secondary generators,supercapacitances, systems of modulation of light. The introduction of aweak ionic conductivity in the usual materials (polymers, combustibleliquids), enables to disperse electrostatic charges.

Derivatives which are derived from coordination anions of the type BF₄⁻, PF₆ ⁻, AsF₆ ⁻, are mainly known, however, they have a limitedstability due to dissociation equilibrium releasing the fluoride ion andthe corresponding Lewis acid, both causing parasite reactions andpresenting a toxicity which is not negligible. The perchlorate anionClO₄ ⁻is thermally unstable and dangerous. On the other hand, anionsderived from bis(perfluoroalkylsulfonyl)imides which present interestingproperties are known. However, this type of chemistry is relativelydifficult to control, in particular during the preparation of precursorsof the type R_(F)SO₂—.

On the other hand, pyrimidinetrione (barbituric acid) and itsderivatives which are obtained by replacing an atom of oxygen by an atomof sulfur (thiobarbituric acid) are known. Also known is the possibilityto produce salts with 2,2-dimethyl-1,3-dioxane-4,6-dione (“Meldrumacid”). In both cases, the acids are relatively weak (pK_(A)) of theorder of 5 in water, of the order of 10 in dimethylsulfoxide). Theirsalts are neither easily soluble nor easily dissociable in organicsolvents. In the case of pyrimidinetrione, the hydrogen bonds formed bythe protons associated with nitrogen reinforce this insolubility. Theirsubstitution with alkyl radicals strongly decreases the strength of theacid.

The inventors have now found that, surprisingly, the solubility anddissociation of the salts obtained from pyridiminandrione derivativesand its homologues by substitution on the carbon atom in position 5, oron the nitrogens in positions 1 and 3 is considerably increased when thesubstituents have an electronically attracting power. The same is truewith respect to compounds derived from 1,3-dioxane-4,6-diones and theirhomologues which carry a substituent which is an electroattractor oncarbon 2 and/or carbon 5. The choice of substituents and the numerouspossible combinations in three substitution sites for each family givevarious materials for which it is possible to modulate the physical orchemical properties to a large extent. These compounds have interestingproperties for the above-mentioned applications and their preparationcalls for materials which are more readily accessible. For example, itis possible to obtain stable anionic heterocycles incorporating smallerquantities of fluorine, or to use as starting products fluorinatedcompounds which are easily accessible. Certain compounds may totallyprevent having to rely on fluorine atoms.

A compound of the present invention comprises at least one anionic partassociated to at least one cationic part M in sufficient number toensure an electronic neutrality of the assembly. It is characterized inthat M is an hydroxonium, a nitrosonium NO⁺, an ammonium —NH₄ ⁺, ametallic cation having a valence m, an organic cation having a valence mor an organometallic cation having a valence m, and in that the anionicpart is an aromatic heterocycle corresponding to one of the formulae

in which:

Y₁, Y₂, Y₃, Y₄ and Y₅ represent independently from one another acarbonyl group, a sulfonyl group, a thiocarbonyl group, a thionyl group,a —C(═NCN)— group or a —C(═C(CN)₂)— group;

Z represents an electroattractor radical having a Hammett parameter atleast equal to that of a fluorine atom;

each of the substituents R_(A), R_(B), R_(C) and R_(D) representsindependently from one another a monovalent or trivalent organicradical, or is part of a polymer chain, one at least of the substituentsR_(C) and R_(D) being a perfluorinated radical. Preferably, the organicradical has 1 to 20 carbon atoms.

In a compound of the present invention, the cation may be a metalliccation selected from alkali metal cations, alkali-earth metal cations,transition metal cations, trivalent metal cations, rare earth cations.By way of example, there may be mentioned Na⁺, Li⁺, K⁺, Sm³⁺, La³⁺,Ho³⁺, Sc³⁺, Al³⁺, Yb³⁺, Lu³⁺, Eu³⁺.

The cation may also be an organometallic cation, for example ametallocenium. By way of example, there may be mentioned cations derivedfrom ferrocene, titanocene, zirconocene, an indenocenium or ametallocenium arene, cations of transition metals complexed with ligandsof the phosphine type possibly having a chirality, organometalliccations having one or more alkyl or aryl groups covalently fixed to anatom or a group of atoms, such as methylzinc, phenylmercury, trialkyltinor trialkyllead cations. The organometallic cation may be part of apolymer chain.

According to a variant of the invention, the compounds of the inventionhave an organic cation selected from the group consisting ofR₃O⁺(oxonium), NR₄ ⁺(ammonium), RC(NHR₂)₂ ⁺(amidinium), C(NHR₂)₃⁺(guanidinium), C₅R₆N⁺(pyridinium), C₃R₅N₂ ⁺(imidazolium), C₃R₇N₂⁺(imidazolinium), C₂R₄N₃ ⁺(triazolium), SR₃ ⁺(sulfonium), PR₄⁺(phosphonium),IR₂ ⁺(iodonium), (C₆R₅)₃C⁺(carbonium). In a given cation,the radicals R may all be identical. However, a cation may also includeradicals R which are different from one another. A radical R may be an Hor it is selected from the following radicals:

alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl,thia-alkyl, thia-alkenyl, sila-alkyl, sila-alkenyl, aryl, arylalkyl,alkyl-aryl, alkenyl-aryl, dialkylamino and dialkylazo radicals;

cyclic or heterocyclic radicals possibly comprising at least one lateralchain comprising heteroatoms such as nitrogen, oxygen, sulfur;

cyclic or heterocyclic radicals possibly comprising heteroatoms in thearomatic nucleus;

groups comprising a plurality of aromatic or heterocyclic nuclei,condensed or non-condensed, possibly containing at least one hydrogen,oxygen, sulfur or phosphorus atom.

When an onium cation carries at least two radicals R which are differentfrom H, these radicals may together form an aromatic or non-aromaticcycle, possibly enclosing the center carrying the cationic charge.

When the cationic part of a compound of the invention is an oniumcation, it may be either in the form of an independent cationic groupwhich is only bound to the anionic part by the ionic bond between thepositive charge of the cation and the negative charge of the anionicpart. In this case, the cationic part may be part of a recurring unit ofa polymer.

An onium cation may also be part of the radical Z carried by the anionicaromatic nucleus. In this case, a compound of the invention constitutesa zwitterion.

When the cation of a compound of the invention is an onium cation, itmay be selected so as to introduce in the compound substituents enablingto confer to said compound specific properties. For example, the cationM⁺ may be a cationic heterocycle with aromatic character, including atleast one nitrogen atom which is alkylated in the cycle. By way ofexample, there may be mentioned an imidazolium, a triazolium, apyridinium, a 4-dimethylamino-pyridinium, said cations possibly carryinga substituent on the carbon atoms of the cycle. Among these cations,those which give an ionic compound according to the invention in whichthe melting point is lower than 150° C. are particularly preferred. Sucha compound having a low melting temperature is particularly useful forpreparing materials with protonic conduction. A particularly preferredmaterial with protonic conduction comprises a compound according to theinvention in which the cation is formed by the addition of a proton onthe nitrogen or an imidazole or a triazole, as well as the correspondingnitrogenated base in a proportion of 0.5 to 10 in molar ratio.

A compound of the invention in which the cation M is a cationic grouphaving a bond —N═N—, —N═N⁺, a sulfonium group, an iodonium group, or asubstituted or non-substituted arene-ferrocenium, possibly incorporatedin a polymeric network, is interesting in as much as it is activatableby a source of actinic energy of appropriate wavelength. Specificexamples of such compounds include those in which the cation is adiaryliodonium cation, a dialkylaryliodonium cation, a triarylsulfoniumcation, a trialkylaryl sulfonium cation, or a substituted ornon-substituted phenacyl-dialkyl sulfonium cation. The above-mentionedcations may be part of a polymer chain.

The cation M of a compounds of the invention may include a group2,2′[azobis(2-2′-imidazolinio-2-yl)propane]²⁺ or2,2′-azobis(2-amidiniopropane)²⁺. The compound of the invention is thencapable of releasing, under the action of heat or an ionizing radiation,radicals which enable to initiate reactions of polymerization, ofcross-linking or, in a general manner, chemical reactions involving freeradicals. Moreover, these compounds are easily soluble in polymeric andmonomeric organic solvents of the same polarity, contrary to thederivatives of anions of the type Cl⁻ which are usually associated withthese types of compounds. They present, on the other hand, a negligiblevapor pressure contrary to the other free radical initiators of theperoxide or azo type, which is a considerable advantage for preparingpolymers in thin films, the volatility of the initiator having as aconsequence a bad polymerization or cross-linking of the surface of thefilm.

The choice of substituents enables to adjust the properties of an ioniccompound of the invention.

According to an embodiment of the invention, the substituents R_(A) andR_(B) on the one hand, one of the substituents R_(C) and R_(D) on theother hand, may independently from one another be an alkyl, an alkenyl,an oxa-alkyl, an oxa-alkenyl, an aza-alkyl, an aza-alkenyl, athia-alkyl, a thia-alkenyl radical, said radicals possibly carrying atleast one aryl group.

b) an aryl possibly carrying at least one radical as defined in a);

c) an alicyclic radical or an aromatic radical possibly carrying atleast one lateral chain comprising a heteroatom or possibly comprisingat least one heteroatom in the cycle;

d) a radical as defined above in a), b) and c) and additionally carryinghalogen atoms, in halogenated or perhalogenated form.

Among the above radicals, alkyl radicals and alkenyl radicals having 1to 10 carbon atoms, halogenated or perhalogenated alkyl or alkenylradicals having 1 to 10 carbon atoms, and oxa-alkyl or oxa-alkenylradicals having 1 to 10 carbon atoms are particularly preferred.

The substituent Z may be selected from the group consisting of —F, —Cl,—Br, —CN, —NO₂, —SCN and —N₃. Z may also be a —C_(n)F_(2n+1),—O—C_(n)F_(2n+1), —S—C_(n)F_(2n+1), —CH₂—C_(n)F_(2n+1), OCF═CF₂ or—SCF═CF₂ radical, 1≦n≦8. In addition, Z may be a radical which comprisesa heterocycle derived from pyridine, pyrazine, pyrimidine, oxadiazole orthiadiazole, which is fluorinated or non-fluorinated.

According to another embodiment, Z is a radical R_(E)Y_(E)— or a radicalR_(E)R_(G)PO— in which Y_(E) represents a carbonyl group, a sulfonylgroup, or a thionyl group, and R_(E) and R_(G) represent independentlyfrom one another a halogen or an organic radical. The substituentscomprising a sulfonyl group are particularly preferred. Each of thesubstituents R_(E) and R_(G) may represent an alkyl, alkenyl, oxa-alkyl,oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl, aryl,alkylaryl, alkenylaryl, arylalkyl, arylalkenyl radical, an alicyclicradical or an aromatic radical possibly carrying at least one lateralchain comprising a heteroatom or possibly comprising at least oneheteroatom in the cycle, said R_(E) and R_(G) may be halogenated orperhalogenated.

According to an embodiment, R_(E) and R_(G) are selected independentlyfrom one another from alkyl or alkenyl radicals having 1 to 12 carbonatoms and possibly comprising at least one heteroatom O, N or S in themain chain or in a lateral chain, and carrying a hydroxy group, acarbonyl group, an amine group, a carboxyl group.

R_(E) and R_(G) may also be selected independently from one another fromaryl, arylalkyl, alkylaryl or alkenylaryl radicals, in which thearomatic nuclei, possibly condensed, comprise heteroatoms such asnitrogen, oxygen, sulfur.

In a particular embodiment, one of the groups R_(E) or R_(G) may be aradical having an iodonium group, a sulfonium, oxonium, ammonium,amidinium, guanidinium, pyridinium, imidazolium, imidazolinium,traizolium, phosphonium or carbonium group, said ionic group totally orpartially acting as cation M. The compound of the invention thenconstitutes a zwitterion.

When R_(E) or R_(G) includes at least one ethylenic unsaturation and/ora condensable group and/or a group which is thermally, photochemicallyor ionically dissociable, the compounds of the invention are reactivecompounds which may be subject to polymerizations, cross-linkings orcondensations, possibly with other monomers. They may also be used tofix ionophorous groups on polymers carrying the reactive function.

A substituent R_(E) or R_(G) may be a mesomorphous group, or achromophore group or a self-doped electronically conducting polymer or ahydrolyzable alkoxysilane.

A substituent R_(E) or R_(G) may include a group capable of trappingfree radicals such as for example a hindered phenol or a quinone.

A substituent R_(E) or R_(G) may also include a dissociating dipole suchas, for example, an amide function, a sulfonamide function or a nitrilefunction.

A substituent R_(E) or R_(G) may also include a redox couple, forexample a disulfide group, a thioamide group, a ferrocene group, aphenothiazine group, a bis(dialkylaminoaryl) group, a nitroxide group oran aromatic imide group.

A substituent R_(E) or R_(G) may include either a complexing ligand oran optically active group.

A substituent R_(E)—Y_(E)— represents an amino acid, or an optically orbiologically active polypeptide.

According to another variant, a compound according to the inventioncomprises a substituent Z which represents a radical having a valency vhigher than two, itself including at least one of the anionic aromaticheterocyclic groups

In this case, the negative charges present on the anionic part of thecompound of the invention may be compensated by the appropriate numberof cations or cationic ionophorous groups M.

According to a particular embodiment, the multivalent radical Z is abivalent radical comprising at least one —SO₂—, one —CO— group, oneperfluoroalkylene group having 2 to 8 carbon atoms, one phenylene grouppossibly substituted by heteroatoms, a redox group —(W═W)_(n)— or acationic group —(W═W)_(n—W) ⁺— in which W represents a nitrogen atom ora group —C(R)—, R representing an hydrogen atom or an organic radicaland 0≦n≦5. The presence of the cationic group —(W═W)_(n)—W⁺— gives tothe compound of the invention colouring properties which are very usefulfor lasers. R preferably has 1 to 8 carbon atoms, or two radicals Rcarried by adjacent carbon atoms forming a cycle. According to anembodiment, Z is part of a recurring unit of a polymer chain. Thecompound of the invention then presents polyelectrolyte properties.

R_(E) or R_(G) may also be part of a poly(oxyalkylene) radical or apolystyrene radical.

A compound of the present invention in which the anion corresponds tothe above general formula A may be prepared according to the followingreaction schemes:

A compound of the present invention in which the anion corresponds tothe above general formula B may be prepared by the following reactionscheme:

In all cases:

L represents a starting electronegative groups selected from F, Cl, Br,N-imidazoyl, N-triazoyl, R_(F)—O—, R_(F)CH₂—O— and R_(F)SO_(X)—, R_(F)being a perfluoroalkyl radical;

A represents a cation M⁺, a triallyl-sylyl group, a trialkyl germanylgroup, a trialkylstannyl group or a tertioalkyl group, in which thealkyl substituents have 1 to 6 carbon atoms.

It is advantageous in the case where A=G to permit a displacement of thereaction in the direction of the formation of the compound of theinvention by addition of a tertiary or hindered base T capable offorming the salt L—[HT⁺] by combination with the proton.

The preferred tertiary bases are in particular selected fromalkylamines, for example triethylamine, di-isopropylethylamine,quinuclidine; 1,4 diazabicyclo[2,2,2]octane (DABCO); pyridines, forexample pyridine, alkylpyridines, dialkylaminopyridines; imidazoles, forexample N-alkylimidazoles, imidazo[1,2,-a]pyridine; amidines, forexample 1,5 diazabicyclo[4,3,O]non-5-ene (DBN), 1,8diazabicyclo[5,4,0]undec-7-ene (DBU); guanidines, for exampletetramethyl guanidine, 1,3,4,7,8-hexahydro-1-methyl-2H-pyrimido[1,2-a]-pyrimidine (HPP).

The use of a compound R_(C)—C(O—A)₂—R_(D) in which A is a tertioalkylgroup is advantageous, since such a group is a proton precursor byformation of the corresponding alkene according to the reaction(CH₃)₃C—→(CH₃)₂C—CH₂+H—.

The use of a compound R_(C)—C(O—A)₂—R_(D) in which A is a trialkylsilylgroup is especially interesting when the starting group is a fluorineatom, by reason of the very high stability of the bond F—Si.

In all these compounds, X represents —CH— or —C(Z)—. The compoundsobtained with X═CH may then be modified by substitution of the residualproton, for example, by action of trifluoromethane sulfonic anhydride.

In the case where at least one of the Y₁ is a group —C(═NCN)— or a group—C(═C(CN)₂)—, the processes to obtain these groups are known to oneskilled in the art. By way of example, the reaction of a carbonyl groupwith cyanamide or malononitrile may be mentioned.

The ionic compounds of the present invention comprise at least oneionophorous group on which substituents which may be quite diverse arefixed. Bearing in mind the large possible choice of substituents, thecompounds of the invention enable to produce properties of ionicconduction in most liquid or polymer organic media having a polarity,even low. The applications are important in the field ofelectrochemistry, in particular for storing energy in primary or ssecondary generators, in supercapacitances, in combustible batteries andin electroluminescent diodes. The compatibility of the ionic compoundsof the invention with polymers or organic liquids enable to producenoted antistatic properties, even when the content of ionic compound isextremely low. The compounds of the invention which are polymers, aswell as polymeric compounds obtained from compounds of the inventionhaving the property of self polymerization or copolymerization, have theabove-mentioned properties with the advantage of having a fixed anioniccharge. This is why another object of the present invention consists inan ionically conductive material consisting of an ionic compound of thepresent invention in solution in a solvent.

According to an embodiment, the ionic compound used for preparing anionically conducting material is selected from compounds in which thecation is ammonium, or a cation derived from a metal, in particular,lithium or potassium, zinc, calcium, rare earth metals, or an organiccation, such as a substituted ammonium, an imidazolium, a triazolium, apyridinnium, a 4-dimethylamino-pyridinium, said cations possiblycarrying a substituent on the carbon atoms of the cycle. The ionicallyconducting material thus obtained has an elevated conductivity andsolubility in solvents, due to low interactions between the positivecharge and the negative charge. Its range of electrochemical stabilityis wide, and it is stable in reducing as well as oxidizing media.Moreover, the compounds which have an organic cation and a melting pointlower than 150° C., in particular compounds of imidazolium, triazolium,pyridinium, 4-dimethyl-amino-pyridinium have an intrinsic elevatedconductivity, even in the absence of solvent, when they are in moltenphase.

The properties of the ionically conducting material may also be adaptedby the choice of substituents R_(A), R_(B), R_(C), R_(D), R_(E) andR_(G).

The choice for at least one of the substituents R_(A), R_(B), R_(C),R_(D), R_(E) or R_(G) of an alkyl group, an aryl group, an alkylarylgroup or an arylalkyl group enables to induce in the ionicallyconductive material properties of the type mesogene, in particular alkylgroups of 6 to 20 carbon atoms, arylalkyl groups, in particular thosecontaining a biphenyl unit which produce phases of the type liquidcrystal. Properties of conduction in phases of the type liquid crystal,nematic, cholesteric or discotic, are interesting for applicationsrelative to optical postings or to reduce the mobility of the anions inthe electrolyte, in particular in polymer electrolytes, withoutaffecting the mobility of the cations. This particularity is importantfor applications in electrochemical generators, in particular thoseinvolving lithium cations.

When Z is a mesomorphous group or a group comprising at least oneethylenic unsaturation and/or a condensable group and/or a group whichis thermally, photochemically or ionically dissociable, the ionicallyconductive material easily forms polymers or copolymers which arepolyelectrolytes, intrinsically when the polymer carries the solvatinggroups, or by addition or a polar solvent of the liquid or polymer type,or by mixture with such a solvent. These products have a conductivitywhich is solely due to the cations, which constitutes a very usefulproperty for applications of the electrochemical generator type. Whenused in low molar fraction in a copolymer, they induce stable antistaticproperties which are little dependent on humidity and promote thefixation of cationic colouring materials, this property being useful fortextile fibers and lasers with colouring materials.

The presence of a substituent Z which is a self-doped electronicallyconductive polymer improves the stability of the ionically conductivematerial with respect to exterior agents. The conductivity is stable intime, even at elevated temperatures. In contact with metal, thesematerials give interface resistances which are very weak and inparticular protect ferrous metals or aluminum against corrosion.

When a Z is a hydrolyzable alkoxysilane, the ionically conductivematerial may form stable polymers by the simple mechanism ofhydrolysis-condensation in the presence of water, thereby enabling totreat surfaces of oxides, silica, silicates, in particular glass, toproduce properties of surface conduction, antistatic properties, or topromote the adhesion of polar polymers.

When a substituent Z is a group comprising a free radical trap such as ahindered phenol, or a quinone, the ionically conductive material has thefollowing advantages and properties: it acts as antioxidant with novolatility and is compatible with polar monomers and polymers, to whichit additionally gives antistatic properties.

When Z comprises a dissociating dipole such as an amide, a sulfonamideor a nitrile, the ionically conductive material has an improvedconductivity in media of low and medium polarity, in particular insolvating polymers which enables to minimize, even to suppress, theaddition of solvents or volatile plasticizing agents.

The presence of a substituent Z which contains a redox couple such as adisulfide, a thioamide, a ferrocene, a phenothiazine, a groupbis(dialkylaminoaryl), a nitroxide, an aromatic imide, enables toproduce in the ionically conductive material, properties of a redoxshuttle which are useful as an element of protection and equalization ofcharge of electrochemical generators, in photoelectrochemical systems,in particular for the conversion of light into electricity in systems ofmodulation of light of the electrochrome type.

The presence of a substituent Z which is a complexing ligand in anionically conductive material enables to chelate metallic cations, inparticular those which possess an elevated charge (2, 3 and 4), in theform of soluble complex in organic media, including in aprotic media,and enables the transport of these cations in particular in the form ofanionic complex, in solvating polymers. The metallic cations of elevatedcharge are indeed immovable in solvating polymers. This type ofcomplexing gives with certain cations of transition metals (Fe, Co . . .) or certain rare earths (Ce, Eu . . . ) particularly stable redoxcouples.

The ionically conductive materials containing a compound of theinvention in which at least one of the substituents R_(A), R_(B), R_(C),R_(D), R_(E) or R_(G) is an alkyl or alkenyl substituent which containsat least one heteroatom selected from O, N or S have a complexing andplasticizing capacity, in particular in polar polymers and especiallypolyethers. The heteroatoms N and S are selectively complexing forcations of transition metals, Zn and Pb.

When a substituent alkyl or alkenyl R_(E) or R_(G) additionally carriesan hydroxy group, a carbonyl group, an amine group, a carboxyl group, anisocyanate group or a thioisocyanate group, the ionic compound of theinvention may give by polycondensation a polymer or a copolymer and theionically conductive material which contains such a polymer or copolymerhas the properties of a polyelectrolyte.

The presence, in the ionically conductive material of the invention, ofa compound in which a substituent R_(E) or R_(G) is selected from aryl,arylalkyl, alkylaryl, alkylaryl or alkenylaryl radicals, in which thelateral chains and/or the aromatic nuclei comprise heteroatoms such asnitrogen, oxygen, sulfur, improves dissociation and increases thepossibility of forming complexes depending on the position of theheteroatom (pyridine) or the possibility to give by duplicativeoxidation conjugated polymers or copolymers (pyrrole, thiophene).

When the ionically conductive material contains a compound of theinvention in which a substituent Z represents a recurring unit of apolymer chain, the material constitutes a polyelectrolyte.

A compound of the invention in which the substituent Z is selected fromthe group consisting of —OC_(n)F_(2n+1), —OC₂F₄H, —SC_(n)F_(2n+1) and—SC₂F₄H, —OCF═CF₂, —SCF═CF₂, n being a whole number from 1 to 8, is aprecursor of stable monomers and polymers, in particular towards oxygeneven at temperatures higher than 80° C. when dealing with polymers. Anionically conductive material which contains such a compound istherefore particularly suitable as the electrolyte of a combustiblebattery.

An ionically conductive material of the present invention comprises anionic compound of the present invention in solution in a solvent.

The solvent may be an aprotic liquid solvent, a polar polymer or amixture thereof.

The aprotic liquid solvent is selected for example from linear ethersand cyclic ethers, esters, nitrites, nitro derivatives, amides,sulfones, sulfolanes, alkylsulfamides and partially halogenatedhydrocarbons. The solvents which are particularly preferred arediethylether, dimethoxyethane, glyme, tetrahydrofurane, dioxane,dimethyltetrahydrofurane, methyl or ethyl formate, propylene or ethylenecarbonate, alkyl carbonates (such as dimethyl carbonate, diethylcarbonate and methylpropyl carbonate), butyrolactones, acetonitrile,benzonitrile, nitromethane, nitrobenzene, dimethylformamide,diethylformamide, N-methylpyrrolidone, dimethylsulfone, fetramethylenesulfone and tetraalkylsulfonamides, having 5 to 10 carbon atoms.

The polar polymer may be selected from cross-linked or non-cross-linkedsolvating polymers, which may carry grafted ionic groups. A solvatingpolymer is a polymer which includes solvating units containing at leastone heteroatom selected from sulfur, oxygen, nitrogen and fluorine. Byway of example of solvating polymers, there may be cited polyethers oflinear structure, comb or blocks, which may form a network, based onpoly(ethylene oxide), or copolymers containing the unit ethylene oxideor propylene oxide or allylglycidylether, polyphosphazenes, cross-linkednetworks based on polyethylene glycol cross-linked with isocyanates ornetworks obtained by polycondensation and carrying groups which enablethe incorporation of cross-linkable groups. Block copolymers in whichcertain blocks carry functions which have redox properties may also becited. Of course, the above list is non-limiting, and all the polymershaving solvating properties may be used.

An ionically conductive material of the present invention maysimultaneously comprise an aprotic liquid solvent selected from theaprotic liquid solvents mentioned above and a polar polymer solventcomprising units containing at least one heteroatom selected fromsulfur, nitrogen, oxygen and fluorine. It may comprise from 2 to 98%liquid solvent. By way of example of such a polar polymer, polymerswhich mainly contain units derived from acrylonitrile, vinylidenefluoride, N-vinylpyrrolidone or methyl methacrylate may be mentioned.The proportion of aprotic liquid in the solvent may vary from 2%(corresponding to a plasticized solvent) to 98% (corresponding to agelled solvent).

An ionically conductive material of the invention may additionallycontain a salt which is well known to be used in the prior art forpreparing ionically conductive material. Among the salts which may beused in admixture with an ionic compound of the invention, a saltselected from perfluoroalcanesulfonates,bis(perfluoroalkylsulfonyl)imides, bis(perfluoroalkylsulfonyl)methanesand tris(perfluoroalkylsulfonyl)methanes are particularly preferred.

Of course, an ionically conductive material of the invention mayadditionally contain additives known to be used in this type of materialand for example mineral or organic charges in the form of powder orfibers.

An ionically conductive material of the invention may be used aselectrolyte in an electrochemical generator. Thus, another object of thepresent invention is an electrochemical generator comprising. a negativeelectrode and a positive electrode both separated by an electrolyte,characterized in that the electrolyte is an ionically conductivematerial as defined above. According to a particular embodiment, such agenerator comprises a negative electrode consisting of metallic lithium,or an alloy thereof, possibly in the form of nanometric dispersion inlithium oxide, or a double nitride of lithium and a transition metal, oran oxide of low potential having the general formulaLi_(1+y+x/3)Ti_(2−x/3)O₄(0≦x≦1, 0≦y≦1), or carbon and carbonatedproducts derived from the pyrolysis of organic materials. According toanother embodiment, the generator comprises a positive electrodeselected from vanadium oxides VO_(x)(2≦x≦2,5), LiV₃O₈,Li_(y)Ni_(1−x)Co_(x)O₂, (0≦x≦1; 0≦y≦1), spinels of manganeseLi_(y)Mn_(1−x)M_(x)O₂(M=Cr, Al, V, Ni, 0≦x≦0,5; 0≦y≦2), organicpolydisulfides FeS, FeS₂, iron sulfate Fe₂(SO₄)₃, phosphates andphosphosilicates of iron and lithium of olivine structure, orsubstituted products wherein iron is replaced by manganese, used aloneor in admixtures. The collector of the positive electrode is preferablyaluminum.

An ionically conductive material of the present invention may also beused in a supercapacitance. Another object of the present invention isconsequently a supercapacitance utilizing at least one carbon electrodeof high specific surface, or an electrode containing a redox polymer inwhich the electrolyte is an ionically conductive material such asdefined above.

An ionically conductive material of the present invention may also beused for doping p or n an electronically conductive polymer and this useconstitutes another object of the present invention.

In addition, an ionically conductive material of the present inventionmay be used as an electrolyte is an electrochrome device. Anelectrochrome device in which the electrolyte is an ionically conductivematerial according to the invention is another object of the presentinvention.

It has been observed that the strong dissociation of ionic species ofthe compounds of the invention results in a stabilization ofcarbocations, in particular those in which there is a conjugation withoxygen or nitrogen and, surprisingly, by a strong activity of the protonform of the compounds of the invention on certain monomers. The presentinvention also has as an object the use of ionic compounds asphotoinitiators as sources of Bronsted acid which are catalysts for thepolymerization or cross-linking of monomers or prepolymers capable ofcationic reaction, or as catalysts for the modification of polymers.

The process of polymerization or cross-linking of monomers orprepolymers capable of cationic reaction is characterized in that thereis used a compound of the invention as photoinitiator constituting asource of acid catalyzing the polymerization reaction. The compoundsaccording to the invention in which the cation is a group having a bond—N═N⁺, —N═N—, a sulfonium group, an iodonium group, or anarene-ferrocenium cation which is substituted or non-substituted.possibly incorporated in a polymeric network, are particularlypreferred.

The choice of the various substituents is made so as to increase thesolubility of said compound in the solvents used for the reaction ofmonomers or prepolymers, and as a function of the desired properties forthe final polymer. For example, the choice of non-substituted alkylradicals gives a solubility in low polar media. The choice of radicalscomprising an oxa group or a sulfone will give a solubility in polarmedia. The radicals including a sulfoxide group, a sulfone group, aphosphine oxide group, a phosphonate group, respectively obtained by theaddition of oxygen on the atoms of sulfur or phosphorus, may give to thepolymer obtained improved properties with respect to adhesion, shine,resistance to oxidation or to WV. The monomers and prepolymers which maybe polymerized or cross-linked with the photoinitiators of the presentinvention are those which may undergo a cationic polymerization.

Among the monomers, those which include a cyclic ether function, acyclic thioether function or cyclic amine function, vinyl compounds(more particularly vinyl ethers), oxazolines, lactones and lactames maybe mentioned.

Among the polymers of the ether or cyclic thioether type, ethyleneoxide, propylene oxide, oxetane, epichlorhydrin, tetrahydroflrane,styrene oxide, cyclohexene oxide, vinylcyclohexene oxide, glycidol,butylene oxide, octylene oxide, glycidyl ethers and esters (for exampleglycidyl methacrylate or acrylate, phenyl glycidyl ether,diglycidylether of bisphenol A or its fluorinated derivatives), cyclicacetals having 4 to 15 carbon atoms (for example dioxolane, 1,3-dioxane,1,3-dioxepane) and spiro-bicyclo dioxolanes may be mentioned.

Among vinyl compounds, vinyl ethers constitute a very important familyof monomers which are capable of cationic polymerization. By way ofexample, there may be mentioned ethyl vinyl ether, propyl vinyl ether,isobutyl vinyl ether, octadecyl vinyl ether, ethyleneglycol monovinylether, diethyleneglycol divinyl ether, butanediol monovinyl ether,butanediol divinyl ether, hexanediol divinyl ether, ethyleneglycol butylvinyl ether, triethyleneglycol methyl vinyl ether, cyclohexanedimethanolmonovinyl ether, cyclohexanedimethanol divinyl ether, 2-ethylhexyl vinylether, poly-THF-divinyl ether having a molecular weight between 150 and5,000, diethyleneglycol monovinyl ether, trimethylolpropane trivinylether, aminopropyl vinyl ether, 2-diethylaminoethyl vinyl ether.

Other vinyl compounds may include, by way of example,1,1-dialkylethylenes (for example isobutene), vinyl aromatic monomers(for example styrene, α-alkylstyrenes, such as α-methylstyrene,4-vinylanisole, acenaphthene) N-vinyl compounds (for examplesN-vinylpyrolidone or N-vinyl sulfonamides).

Among prepolymers, there may be mentioned compounds in which epoxygroups are carried by an aliphatic chain, an aromatic chain, or aheterocyclic chain, for example glycidic ethers of bisphenol A which areethoxylated by 3 to 15 ethylene oxide units, siloxanes having lateralgroups of the epoxycyclohexene-ethyl type obtained by hydrosilylation ofcopolymers of dialkyl, alkylaryl or diaryl siloxane with methylhydrogenosiloxane in the presence of vinylcyclohexene oxide,condensation products of the sol-gel type obtained from triethoxy ortrimethoxy silapropylcyclohexene oxide, urethanes incorporating thereaction products of butanediol monovinylether and an alcohol of afunctionality higher than or equal to 2 with an aliphatic or aromaticdi- or tri-isocyanate.

The process of polymerization according to the invention consists inmixing at least one monomer or prepolymer capable of cationicpolymerization and at least one ionic compound of the invention, andsubjecting the mixture obtained to actinic or β radiation. Preferably,the reaction mixture is subjected to radiation after having been formedinto a thin layer having a thickness lower than 5 mm, preferably in theform of a thin layer having a thickness lower than or equal to 500 μm.The duration of the reaction depends on the thickness of the sample andthe power of the source at the active λ wavelength. It is defined by thespeed at which it passes in front of the source, which is between 300m/min and 1 cm/min. Layers of the final material having a thicknesshigher than 5 mm may be obtained by repeating many times the operationconsisting in spreading a layer and treating it with radiation.

Generally, the quantity of photoinitiator used is between 0.01 and 15%by weight with respect to the weight of the monomer or prepolymer,preferably between 0.1 and 5% by weight.

An ionic compound of the present invention may be used as photoinitiatorin the absence of solvent, for example when it is intended to polymerizeliquid monomers in which the ionic compound used as photoinitiator issoluble or easily dispersible. This type of utilization is particularlyinteresting, since it enables to overcome the problems associated withsolvents (toxicity, flammability).

An ionic compound of the present invention may also be used asphotoinitiator in the form of a homogeneous solution in a solvent whichis inert towards polymerization, ready to be used and easilydispersible, in particular in the case where the medium to bepolymerized or cross-linked has a high viscosity.

As example of an inert solvent, there may be mentioned volatilesolvents, such as acetone, methyl-ethyl ketone and acetonitrile. Thesesolvents will be used merely to dilute the products to be polymerized orcross-linked (to make them less viscous, especially when dealing with aprepolymer). They will be removed by drying after polymerization orcross-linking. Non-volatile solvents may also be mentioned. Anon-volatile solvent also serves to dilute the products that one wishesto polymerize or cross-link, and to dissolve the ionic compound of theinvention used as photoinitiator, however, it will remain in thematerial formed and will thus act as plasticizing agent. By way ofexample, propylene carbonate, γ-butyrolactone, ether-esters of mono-,di-, tri-ethylene or propylene glycols, ether-alcohols of mono-, di-,tri-ethylene or propylene glycols, plasticizing agents such as esters ofphthalic acid or citric acid may be mentioned.

According to another embodiment of the invention, there may be used assolvent or diluent a compound which is reactive towards polymerization,which is a compound of low molecular weight and of low viscosity whichwill simultaneously act as polymerization monomer and solvent or diluentfor more viscous polymers or prepolymers used in combination. After thereaction, these monomers having been used as solvent will be part of themacromolecular network finally obtained, their integration being widerwhen dealing with bi-functional monomers. The material obtained afterirradiation is now free of products having a low molecular weight and asubstantial vapour tension, or capable of contaminating objects withwhich the polymer is in contact. By way of example, a reactive solventmay be selected from mono and divinyl ethers of mono-, di-, tri-,tetra-ethylene and propylene glycols, N-methylpyrolidone,2-propenylether of propylene carbonate commercially available forexample under the commercial designation PEPC from ISP, New Jersey,United States.

To irradiate the reaction mixture, the irradiation may be selected fromultraviolet radiation, visible radiation, X-rays, γ rays and βradiation. When ultraviolet light is used as actinic radiation, it maybe advantageous to add to the photoinitiators of the inventionphotosensitizers intended to provide an efficient photolysis withwavelengths less energetic than those corresponding to the maximum ofabsorption of the photoinitiator, such as those produced by industrialdevices, (1≈300 nm for mercury vapour lamps in particular). Suchadditives are known, and by way of non-limiting example, there may bementioned anthracene, diphenyl-9, 10-anthracene, perylene,phenothiazine, tetracene, xanthone, thioxanthone, acetophenone,benzophenone, 1,3,5-triaryl-2-pyrazolines and derivatives thereof, inparticular derivatives which are substituted on the aromatic nuclei byalkyl, oxa- or aza-alkyl radicals, enabling inter alia to change theabsorption wavelength. Isopropylthioxantone is an example of preferredphotosensitizer when an iodonium salt according to the invention is usedas photoinitiator.

Among the different types of radiation mentioned, ultraviolet radiationis particularly preferred. On the one hand, it is more convenient to usethan the other radiations mentioned. On the other hand, photoinitiatorsare in general directly sensitive towards UV rays and photosensitizersare more efficient when the difference of energy (δλ) is lower.

The ionic compounds of the invention may also be used in associationwith free radical initiators produced thermally or by action of actinicradiation. It is also possible to polymerize or cross-link mixtures ofmonomers or polymers containing functions in which the types ofpolymerization are different. For example, monomers or prepolymers whichpolymerize by free radical and monomers or prepolymers which polymerizeby cationic polymerization. This possibility is particularlyadvantageous to produce interpenetrated networks having physicalproperties which are different from those which would be obtained by asimple mixture of polymers originating from corresponding monomers.Vinyl ethers are not or are very little active by free radicalinitiation. It is therefore possible, in a reaction mixture containing aphotoinitiator according to the invention, a free radical initiator, atleast one monomer of the vinyl ether type and at least one monomercomprising non-activated double bonds such as those of the allyl groups,to carry out a separate polymerization of each type of monomer. On theother hand, it is known that monomers which are lacking in electrons,such as esters or amides of farmaric acid, maleic acid, acrylic ormethacrylic acid, itaconic acid, acrylonitrile, methacrylonitrile,maleimide and derivatives thereof, form in the presence of vinyl etherswhich are enriched in electrons, complexes of transfer of charge givingalternated polymers 1:1 by free radical initiation. An initial excess ofvinyl monomers with respect to this stoichiometry enables to preservepolymerizable functions by pure cationic initiation. The start of theactivity of a mixture of free radical initiator and cationic initiatoraccording to the invention may be carried simultaneously for the tworeactants in the case for example of isolation by actinic radiation of awavelength for which the photoinitiators of the invention and theselected radical initiators are active, for example at 1=250 nm. By wayof example, the following commercial products: Irgacure 184®, Irgacure651®, Irgacure 261®, Quantacure DMB®, Quantacure ITX® may be mentionedas initiators.

It may also be advantageous to use the two types of polymerization in asequential manner, to first form prepolymers which are easy to shape andin which hardening, adhesion, solubility as well as degree ofcross-linking may be modified by initiating the activity of the cationicinitiator. For example, a mixture of a thermo-dissociable radicalinitiator and a cationic photoinitiator according to the inventionenables to provide sequential polymerizations or cross-linking, firstunder the action of heat, then under the action of actinic radiation.Similarly, if a free radical initiator and a cationic photoinitiatoraccording to the invention are selected, the first being photosensitiveat longer wavelengths than the one initiating the photoinitiatoraccording to the invention, there is obtained a cross-linking in twocontrollable steps. Free radical initiators may for example be Irgacure®651 enabling to initiate free radical polymerizations at wavelength of365 nm.

The invention also has as an object the use of ionic compounds of theinvention for chemical amplification reactions of photoresists in thefield of microlithography. During such use, a film of a materialcomprising a polymer and an ionic compound of the invention is subjectto irradiation. The irradiation causes the formation of the acid byreplacement of the cation M with a proton, which catalyzes thedecomposition or transformation of the polymer. After decomposition ortransformation of the polymer on the parts of the film which have beenirradiated, the monomers formed or the polymer which has been convertedare removed and what remains is an image of the unexposed parts. Forthis particular application, it is advantageous to use a compound of theinvention which is in the form of a polymer consisting essentially ofstyrenyl recurring units carrying as substituent an aromatic anionicheterocycle. These compounds enable to obtain after photolysis productswhich are not volatile, and therefore not odoriferous when dealing withsulfides. Among the polymers which may thus be modified in the presenceof a compound of the invention, there may for example be cited polymerscontaining ester units or tertiaryalkyl arylether units, for examplepoly(phthaldehydes), polymers of bisphenol A and a diacide,polytertiobutoxycarbonyl oxystyrene, polytertiobutoxy-a-methyl styrene,polyditertiobutylfimarate-co-allyltrimethyl-silane and polyacrylates ofa tertiary alcohol, in particular tertiobutyl polyacrylate. Otherpolymers are described in J. V. Crivello et al, Chemistry of Materials8, 376-381, (1996).

The ionic compounds of the present invention, which have an elevatedthermal stability, give numerous advantages with respect to the knownsalts of the prior art. They have speeds of initiation and propagationwhich are comparable or higher than those obtained with coordinationanions of the type PF₆ ⁻, AsF₆ ⁻ and especially SbF₆ ⁻.

In the compounds of the present invention, the pairs of ions have a veryhigh dissociation, which enables the expression of intrinsic catalyticproperties of the cation M^(m+), in which the active orbits are easilyexposed to substrates of the reaction, especially in different media.Most of the important reactions of organic chemistry may thus be carriedout under easy conditions, with excellent yields and the possibility ofseparating the catalyst from the reaction mixture. The demonstration ofasymmetric induction by the use of an ionic compound according to theinvention which carries a chiral group is particularly important in viewof its generality and its ease of operation. The present inventionconsequently has as another object the use of compounds of the inventionas catalysts in Friedel-Crafts reactions, Diels-Alder reactions,aldolization reactions, additions of Michael, reactions of allylation,reactions of pinacolic coupling, reaction of glycosilation, reaction ofopenings of the cycle of oxetanes, reactions of metathesis of alkenes,polymerizations of the Ziegler-Natta type, polymerizations of themetathesis type by cycle opening and polymerizations of the metathesistype of acyclic dienes. The preferred ionic compounds of the inventionfor utilization as catalyst for the above reactions are those in whichthe cation is selected from lithium, magnesium, copper, zinc, tin,trivalent metals, including rare earths, platinoids, and theirorganometallic couples, in particular metallocenes.

The compounds of the invention may also be used as solvent to carry outchemical, photochemical, electrochemical, photoelectrochemicalreactions. For this particular use, the ionic compounds in which thecation is an imidazolium, triazolium, pyridinium or4-dimethylamino-pyridinium, are preferred, said cation possibly carryinga substituent on the carbon atoms of the cycle. Among the compoundsbeing used in liquid form, those having a melting point lower than 150°C., more particularly lower than 100° C., are particularly preferred.

The inventors have also found that the anionic charge carried by thepentacyclic group or the group derived from tetrazapentalene exerts astabilizing effect on electronic conductors of the conjugated polymertype, and that use of a compound in which one of the substituentscomprises a long alkyl chain enables to make these polymers soluble inthe usual organic solvents even in doped state. Grafting of thesecharges on the polymer itself gives polymers in which the global chargeis cationic, which are soluble in organic solvents and have, in additionto their stability, properties of anticorrosion towards metals, aluminumand ferrous metals. It is also an object of the present invention toprovide electronically conductive material comprising an ionic compoundof the present invention in which the cationic part is a polycationconstituted of a doped “p” conjugated polymer. The preferred ioniccompounds for this application are those in which one of thesubstituents R_(A), R_(B), R_(C), R_(D), or Z contains at least onealkyl chain having 6 to 20 carbon atoms.

The colouring materials of cationic type (cyanines) are used more andmore frequently as sensitizers of photographic films, for storingoptical information (optical disks accessible in writing), for lasers.The tendency of these conjugated molecules to pile over one another whenthey are in solid phase limits their utilization, because of thevariation of the optical properties with respect to the isolatedmolecule. The use of ionic compounds of the invention for manufacturingcationic colouring materials in which the counter ions, possibly boundto this same molecule, correspond to functions of the invention enablesto reduce phenomenon of aggregation, including in solid polymer matricesand to stabilize these colouring materials. It is another object of thepresent invention to provide a composition of cationic colouringmaterial, characterized in that it contains an ionic compound accordingto the invention. Particularly preferred ionic compounds for thisapplication are those in which the negative charge(s) of the ionic groupare either fixed to the molecule of the colouring material, or theyconstitute the counter-ion of s the positive charges of the colouringmaterial. Other preferred compounds for this application are those inwhich the radical Z is a bivalent radical comprising at least onecationic group —(W═W)_(n)—W⁺—, in which W represents a nitrogen atom ora —C(R)— group (R being an organic radical) and 0≦n≦5.

The present invention is illustrated by the following examples to whichit is however not limited.

EXAMPLE 1

To 9.91 g (100 mmoles) of butyl isocyanate C₄H₉NCO in 30 ml of anhydrousdichloromethane, there is added drop wise, during 30 min, 5.91 g (100mmoles) of propylamine C₃H₇NH₂ diluted in 20 ml of anhydrousdichloromethane. After 2 hours, 14.1 g (100 mmoles) of malonyl chlorideClCOCH₂COCl in 100 ml of anhydrous dichloromethane were added at 0° C.under argon. A release of hydrochloric acid accompanying the reaction ofcyclization was noted. After 48 hours, the solution was evaporated and1-propyl-3-dibutyl-barbituric acid was recovered in quantitative yieldafter drying.

To 11.3 g (50 mmoles) of this compound in solution in 60 ml of anhydroustetrahydrofurane (THF), at −20° C. and under mechanical stirring, thereis added 11.22 g (100 mmoles) of 1,4-diaza-bicyclo[2,2,2]octane (DABCO),and drop wise 8.43 g (100 mmoles) of trifluoromethanesulfonyl chlorideCF₃SO₂Cl. After 24 hours, the reaction mixture was stirred during 4hours with 2.12 g (50 mmoles) of anhydrous lithium chloride. Afterfiltering to remove the precipitate of DABCO hydrochloride, the solventwas evaporated. After drying, the lithium salt of5-trifluoromethanesulfonyl-1-propyl-3-butyl-barbituric was recovered inquantitative yield, with a purity determined by a proton RMN higher than97%.

In the same manner,5-trifluoromethanesulfonyl-1-allyl-3-butyl-barbituric acid was obtainedby replacing propylamine with allylamine.

These salts are soluble in most of the usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in aprotic solvating polymers such as polyethyleneoxide. In the latter solvent at a concentration O/Li of 12/1, they showan ionic conductivity higher than 10⁻⁴ S.cm⁻¹ at a temperature of 60° C.

EXAMPLE 2

134.96 g (1 mole) of sulfuryl chloride ClSO₂Cl diluted in 100 ml ofanhydrous dichloromethane were added drop wise during 1 hour to asolution of 146.23 g (1 mole) of butylamine C₄H₉NH₂ (2 moles) in 500 mlof anhydrous THF at 0° C. The reaction was continued during 2 hours at0° C., and during 3 hours at room temperature. After filtering thereaction mixture to remove the butylamine hydrochloride formed, thesolvent was evaporated by means of a rotary evaporator.

The product obtained was recrystallized in 200 ml of methanol, and 151 gof N,N′-dibutylsulfamide C₄H₉NHSO₂NHC₄H₉ (yield 72%) were recoveredafter filtration and drying, with a purity characterized by a proton RMNhigher than 20 99%. To 20.83 g (100 mmoles) of N,N′-dibutylsulfamide and10.41 g (100 mmoles) of malonic acid in 100 ml of anhydrous acetonitrileat 0° C., there is added 41.27 g of 1,3-dicyclohexylcarbodiimide (200meq). After 2 hours at 0° C. and 24 hours at room temperature, thereaction mixture was filtered to remove the 1,3-dicyclohexylurea formed,and the solvent was evaporated. The product obtained was recrystallizedin 50 ml of methanol containing 9.81 g (100 meq) of potassium acetate.After filtering and drying, 21.7 g of the potassium salt of1,3-dibutyl-2-sulfonyl-barbituric (yield 69%) were recovered, with apurity characterized by a proton RMN higher than 98%.

1,3-dibutyl-2-sulfonyl-barbituric acid was prepared by ether extractionof the potassium salt in water at a pH lower than 2. Then, by aprocedure similar to the one described in Example 1, the lithium salt of5-trifluoromethanesulfonyl-1,3-dibutyl-2-sulfonyl-barbituric acid andthe lithium salt of5-perfluorobutanesulfonyl-1,3-dibutyl-2-sulfonyl-barbituric acid wereobtained by replacing trifluoromethanesulfonyl chloride withperflurobutanesulfonyl fluoride.

Potassium salts were obtained by recrystallizing lithium salt in asaturated solution of potassium chloride.

These salts are soluble in most of the usual organic solvents(tetrahydrofarane, acetonitrile, dimethylforrnamide, ethyl acetate,glymes, . . . ) and in aprotic solvating polymers such as polyethyleneoxide. In the latter solvent. at a concentration O/Li of 12.1, they showan ionic conductivity higher than 2×10⁻⁴ S.cm⁻¹ at a temperature of 60°C. The lithium salts, at a concentration as low as 0.1 g/l in water,decrease the surface tension to a value lower than 25 mN/m.

EXAMPLE 3

16.02 g (100 mmoles) of ethyl malonate C₂H₅OOCCH₂COOC₂H₅ were reactedwith 11.82 g (200 mmoles) of propylamine C₃H₇NH₂. After stirring thesolution during 24 hours, there is obtained a thick paste which, afterdrying, has given a quantitative yield of dipropylamide malonateC₃H₇NHOCCH₂CONHC₃H₇ characterized by a proton RMN. There is then addeddrop wise 6.75 g (50 mmoles) of sulfuryl chloride ClSO₂Cl diluted in 20ml of anhydrous dichloromethane to 9.31 g of dipropylamide malonate (50meq) in solution in 30 ml of pyridine at 0° C. The reaction wascontinued during two hours at room temperature, and during 48 hours atroom temperature and the solvent was evaporated. The product obtainedwas reclaimed in 30 ml of water which has been acidified with 30 ml ofhydrochloric acid 4 M, and extracted twice with 25 ml of ether. Afterdrying the organic phase with magnesium sulfate, evaporating ether anddrying the residue, 11.67 g (94% yield) of1,3-dipropyl-2-sulfonyl-barbituric acid were recovered with a puritycharacterized by a proton RMN higher than 97%.

The potassium salt was obtained by treating the acid with potassiumcarbonate in water.

In 20 ml of anhydrous acetonitrile containing 2.12 g (20 mmoles) ofbromine cyanide BrCN, there is added 2.87 g (20 mmoles) of silverchloride AgCl, then 20 mmoles of 1,3-dipropyl-2-sulfonyl-barbituric acidand 4.49 g (40 mmoles) of 1,4-diazabicyclo[2.2.2]octane (DABCO). After24 hours, the solvent was evaporated and the residue was recrystallizedin a saturated aqueous solution of potassium chloride. After filteringand drying, the following compound was obtained:

By a similar process, 1,3-di trifluoroethyl-2-sulfonyl-barbituric andits potassium salt, and the potassium salt of 5-cyano-1,3-ditrifluoroethyl-2-sulfonyl-barbituric acid were obtained by replacingpropylamine by trifluoroethylamine.

These salts are soluble in most of the usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in aprotic solvating polymers such as polyethyleneoxide. In the latter solvent at a concentration of O/Li of 12/1, theyshow an ionic conductivity higher than 10⁻³ S.cm⁻¹ at a temperature of100° C.

EXAMPLE 4

10.12 g (100 mmoles) of 3-amino-1-propanol vinyl ether CH₂═CHO(CH₂)₃NH₂in 30 ml of anhydrous THF were reacted with 9.91 g (50 mmoles) of1,1′-sulfonyldiimidazole, prepared by reacting imidazole with sulfurylchloride. After 48 hours, the reaction mixture was poured into a flaskcontaining 8.01 g (50 mmoles) of ethyl malonate C₂H₅O—OCCH₂CO—OC₂H₅ and8.1 g (75 mmoles) of sodium methoxide CH₃ONa. After 96 hours at roomtemperature, the solvents were evaporated and a product was reclaimed in30 ml of methanol. After adding 4.91 g (50 mmoles) of potassium acetate(50 meq), a precipitate was formed which was recovered by filtration ona fritted glass of porosity N°3, and washed twice with 5 ml of coldwater. 11.61 g of the potassium salt of1,3-vinyloxypropyl-2-sulfonyl-barbituric acid were obtained after drying(69% yield) characterized by a proton RMN

To 3.7 g (10 mmoles) of this compound in solution in 20 ml of THF at−20° C., there is added 2.01 g (10 mmoles) of1-(trifluoromethanesulfonyl)imidazole (commercially available fromFluka). The reaction was continued during 4 hours at −20° C., and during48 hours at room temperature. The solvent was then evaporated and thesolid residue was washed with dichloromethane to remove the imidazoleformed during the reaction. The following compound was obtained:

On the other hand, 3.7 g (10 mmoles) of the potassium salt of1,3-vinyloxypropyl-2-sulfonyl-barbituric were treated with 1.96 g (10mmoles) of 2,2,2-trifluoroethyl trifluoroacetate in 15 ml of anhydrousTHF. After 24 hours, the solution obtained was evaporated and afterdrying, the potassium salt of5-trifluoroacetyl-1,3-vinyloxypropyl-2-sulfonyl-barbituric acid wasrecovered in quantitative yield.

The homopolymers of these salts prepared by polymerization in anhydrousacetonitrile, initiated by cationic means withbis(trifluoromethane-sulfonyl)imide, have a conductivity at aconcentration of 0.8 M in a mixture of dimethylcarbonate and ethylenecarbonate (2:1) higher than 10⁻³ S.cm⁻¹ at 30° C. Moreover, thesehomopolymers are soluble in most of the usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in aprotic solvating polymers such as polyethyleneoxide.

EXAMPLE 5

In 20 ml of anhydrous THF at −20° C. there is added 29.26 g (40 mmoles)of butylamine and drop wise 23.7 g (20 mmoles) of chloroflurosulfoneFSO₂Cl. After 1 hour, 19.81 g of 2,2,-trifluoroethylamine CF₃CH₂NH₂ (20mmoles) and 2 ml of pyridine were added, and the reaction was continuedduring 2 hours at −20° C. and for 48 hours at room temperature. Thereaction mixture was filtered and the solvent was evaporated. Afterrecrystallization of the residue in methanol,N-2,2,2-trifluoroethyl-n′-butyl-sulfamide was recovered. By a similarprocess, N-2,2,3,3,3-pentafluoropropyl-N′-butyl-sulfamide was preparedby replacing 2,2,2-trifluoroethylamine with2,2,3,3,3-pentafluoropropylamine, andN-2,2,3,3,4,4,4-heptafluorobutyl-N′-butyl-sulfamide was prepared byreplacing 2,2,2-trifluoroethylamine with2,2,3,3,4,4,4-heptafluorobutylamine.

Barbituric acids and potassium salts corresponding to these threecompounds were obtained by a process similar to the one described inExample 2.

Potassium salts of acids carrying a trifluoromethanesulfonyl group inC-5 were obtained by a process similar to the one described in Example4.

These salts are soluble in most of the usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in aprotic solvating polymers.

EXAMPLE 6

By a process similar to Example 3, 5-fluoro-1,3-dibutyl-barbituric acidwas obtained by replacing ethyl malonate with diethyl fluoromalonate(commercially available from Lancaster). The potassium salt was obtainedby dosing the acid with a titrated solution of potassium hydroxide, thepoint of equivalency being obtained by pH metry. After lyophilizationand drying under vacuum, the following compound was obtained inquantitative yield.

By a similar process, 5-fluoro-1,3-di-(2-ethylhexyl)-barbituric acid wasobtained by replacing butylamine with 2-ethylhexylamine.

EXAMPLE 7

Chloro-bis(chlorosulfonyl)-methide ClCH(SO₂Cl)₂ was prepared by themethod described by Fild & Rieck (Chem.-Ztg., (1976), 100(9), 391-2) byreacting chloroacetic acid with phosphoryl chloride POCl₃. In 40 ml ofdichloromethane, there is added 6.25 g (30 mmoles) ofN,N′-dibutylsulfamide, obtained as in Example 2, and 7.42 g ofchloro-bis(chlorosulfonyl)methide. After 48 hours under stirring,dichloromethane was evaporated and the residue was reclaimed in 40 ml ofwater. The lithium salt was obtained by dosing the acid with a titratedsolution of lithium hydroxide, the point of equivalency being determinedby pH-metry, after lyophilization and drying under vacuum, the followingcompound was obtained in quantitative yield:

EXAMPLE 8

To 200 ml of anhydrous dichloromethane at −20° C., under mechanicalstirring and in an atmosphere of argon, containing 20.81 g (200 mmoles)of malonic acid HOOCCH₂COOH and 41.63 g (200 mmoles) ofhexafluoroacetone trihydrate CF₃COCF₃.3H₂O (commercially available fromAldrich), there is slowly added 95.17 g (800 mmoles) of thionyl chlorideSOCl₂ diluted with 100 ml of anhydrous dichloromethane. When theaddition was terminated (about 2 hours), the reaction was continuedduring 24 hours at −20° C. and for 24 hours at room temperature. Thesolvent was then evaporated and the residue was reclaimed in 100 ml ofwater. There is then added in portions 15.2 g (110 mmoles) of anhydrouspotassium carbonate and the precipitate obtained was recrystallizedafter adding 14.91 g (200 mmoles) of anhydrous potassium chloride KCl.After filtering and drying, 35.8 g (71% yield) of the potassium salt of2,2-trifluoromethyl-1,3-dioxolane-4,6-dione (I) were recovered, having apurity determined by a proton RMN higher than 98%.

The lithium salt was obtained by ionic exchange (metathesis) withlithium chloride in THF.

By a similar process except that one single equivalent of thionylchloride was used, there is obtained:

the potassium salt of 2-methyl-2-trifluoromethyl-1,3-dioxolane-4,6-dione(II), by replacing hexafluoroacetone with 1,1,1-trifluoroacetone (98%purity and 65% yield),

the potassium salt of2-methyl-2-hepta-fluoropropyl-2,3-dioxolane-4,6-dione (III), byreplacing hexafluoroacetone with 3,3,4,4,5,5,5-heptafluoro-2-pentanone(97% purity and 71% yield), and

the potassium salt of 2-phenyl-2-trifluoromethyl-1,3-dioxolane-4,6-dione(IV), by replacing hexafluoroacetone with 2,2,2-trifluoroacetophenone(99% purity and 76% yield).

The corresponding acids were prepared by extracting an acid solution ofthe salts with ether.

The potassium salts of the acids carrying a nitrile group in C-5 wereprepared by a process similar to the one described in Example 3.

The potassium salts of the acids carrying a grouptrifluoromethanesulfonyl in C-5 were obtained by a process similar tothe one described in Example 1, the potassium salts of the acidscarrying a 4-styrenesulfonyl in C—S were prepared by a process similarto the one described in Example 1, by replacing trifluoromethanesulfonylchloride with 4-styrenesulfonyl chloride (commercially available fromDajac Monomers & Polymers; the potassium salts of acids carrying aperfluorobutanesulfonyl group in C-5 were prepared by replacingtrifluoromethanesulfonyl chloride with perfluorobutane sulfonylfluoride; the potassium salts of acids carrying aperfluorobutanesulfonyl group in C-5 were prepared by replacingtrifluoromethanesulfonyl chloride with perfluorobutane sulfonylfluoride; and the potassium salts of acids carrying a vinyl sulfonylgroup in C-5 were prepared by replacing trifluoromethanesulfonylchloride with ethylenesulfonyl fluoride (commercially available fromACROS).

In all cases, lithium salts were obtained by ionic exchange (metathesis)between potassium salts and lithium chloride in THF.

EXAMPLE 9

5.38 g (20 mmoles) of dodecylsulfonic acid chloride C₁₂H₂₅SO₂Cl(commercially available from Lancaster) in 30 ml of anhydrous THF and 10ml of pyridine were added to 6.29 g (20 mmoles) of the potassium salt of1,3-dibutyl-2-sulfonyl-barbituric acid, prepared under conditionssimilar to those described in Example 2. After 24 hours, the slightlycoloured solution was filtered to remove the precipitate of potassiumchloride, and contacted with 800 mg of lithium carbonate Li₂CO₃ and 4 gof activated charcoal. The mixture was stirred during 24 hours, and theexcess carbonate and the active carbon were removed by filtering thesolution and the solvent was evaporated. 10.9 g of the lithium salt of5-dodecylsulfonyl-1,3-dibutyl-2-sulfonylbarbituric acid were obtained inquantitative yield and the product is characterized by a proton RMN:

which has noted tensio-active properties, including in aprotic solventsand more particularly in aprotic solvating polymers.

EXAMPLE 10

479 mg (1 mmole) of Rhodamine B were suspended in 10 ml of pyridine and314 mg (1 mmole) of the potassium salt of1,3-dibutyl-2-sulfonyl-barbituric acid, obtained in Example 2, and 206mg (1 mmole) of dicyclohexyl-carbodiimide were added. After 48 hoursunder stirring, the mixture was filtered to remove dicyclohexylurea andwas subjected to evaporation. The compound obtained is a zwitterion:

which has intense colouring properties. It is soluble in polar polymersand enables the production of lasers with colouring materials. Theanionic group grafted on Rhodamine B also enables to be adsorbed onoxides, in particular non-particular titanium dioxide, it then acts as asensitizer towards visible radiation, in particular in applications tophotovoltaic cells.

EXAMPLE 11

To 15 ml of methanesulfonic acid at 0° C., there is added 5.8 g (10mmoles) of the potassium salt of5-perfluorobutanesulfonyl-2-phenyl-2-trifluoromethyl-1,3-dioxolane-4,6-dione,obtained in Example 8, and 3.22 g (10 mmoles) of iodosobenzene diacetateφ-I(OCOCH₃)₂ (commercially available from Lancaster). After 6 hoursunder stirring at 0° C., the reaction mixture was poured into 100 ml ofether, and the precipitate which appeared was recovered by filtrationand dried. The zwitterion obtained:

enables to release, under the effect of actinic radiation (light, γrays, electron beams), an acid which is capable of initiating apolymerization by a cationic mechanism. It is soluble in most of theusual organic solvents (tetrahydrofurane, acetonitrile,dimethyl-formamide, ethyl acetate, glymes, . . . ) and in aproticsolvating polymers such as polyethylene oxide. It is also soluble atmore than 5% by weight in reactive solvents such as triethyleneglycoldivinyl ether.

EXAMPLE 12

2.8 g (10 mmoles) of 4,4′-azobis(4-cyanovaleric), 3.24 g (20 mmoles) ofcarbonyldiimidazole and 100 mg of dimethylamino pyridine were suspendedin 20 ml of ether and kept at 0° C. When CO₂ has ceased to escape (5hours), there is added 1.44 g (20 mmoles) of the potassium salt of2,2-trifluoromethyl-1,3-dioxolane-4,6-dione, obtained in Example 8. Themixture was kept under magnetic stirring at 0° C. during 24 hours. Bycentrifugation, the following crystalline precipitate was isolated:

This salt is soluble in most of the usual organic solvents, inparticular in acetone, acetonitrile, ethyl acetate, tetrahydrofarane,and in aprotic solvating polymers such as polyethylene oxide. It may beused as a non-volatile free radical initiator to initiate polymerizationor cross-linking reactions already at 60° C.

EXAMPLE 13

First, the disodium salt of2,2′-azinobis(3-ethylbenzo-thiazoline-6-sulfonic) acid was prepared fromits diammonium salt (commercially available from Aldrich) by treating itwith a titrated solution of sodium hydroxide. After evaporation anddrying, the disodium salt was recovered in quantitative yield. To 1.12 gof the latter (2 mmoles) in 10 ml of anhydrous acetonitrile, there isslowly added 508 mg of oxalyl chloride ClCOCOCl (4 mmoles) in solutionin 1 ml of anhydrous dichloromethane. After 4 hours under stirring, 4 mlof anhydrous pyridine and 1.47 g (4 mmoles) of the potassium salt of1,3-(2,2,2-trifluoroethyl)-2-sulfonyl-barbituric acid, obtained inExample 3, were added. After 24 hours, acetonitrile was evaporated andthe residue was reclaimed in 10 ml of water. After adding 1.29 g oftetrabutyl ammonium bromide, the precipitate obtained was extracted withdichloromethane. After drying, the organic phase with magnesium sulfate,evaporation of the solvent and drying, the following compound wasobtained:

This compound gives by oxidation a radical and a biradical which arestable zwitterions and it enables to produce oxidation catalyses betweenan oxygenated aqueous phase and an organic phase which is non misciblecontaining the species to be oxidized.

EXAMPLE 14

2.54 g of polyaniline chloride (AC&T, St Egreve, France) were suspendedin 10 ml of water:

There is then added 9.89 g of the potassium salt of5-fluoro-1,3-di-2-ethylhexyl-2-sulfonyl-barbituric acid, obtained inExample 6:

After 48 hours under stirring, a polyaniline doped with5-fluoro-1,3-di-2-ethylhexyl-2-sulfonyl-barbituric acid, soluble intoluene, was recovered. The doped polyaniline thus obtained is anelectronically conductive polymer which has a conductivity, measured bythe method of the four points, of 6 S/cm, stable in humid medium.

From a solution in toluene of doped polyaniline, it was possible toproduce a film on a polypropylene support (PP) treated by Corona effect.After drying under vacuum at 60° C. during 48 hours, a conductivedeposit was obtained which adheres to polyaniline and has a thicknesslower than 1 micron. In addition, this electronically conductive polymeris a good corrosion inhibitor for ferrous metals in acid or chloridemedium. Treatment of surfaces to be protected is carried out simply bydepositing a solution of PCE in the form of a paint, followed by dryingand thermal treatment at 100° C.

EXAMPLE 15

A solution of 17 g (40 mmoles) of the lithium salt of5-(4-styrenesulfonyl)-2,2-trifluoromethyl-1,3-dioxolane-4,6-dione acid,prepared as in Example 6, 3.18 g of acrylonitrile (60 mmoles) and 100 mgof 1,1′-azobis(cyclohexanecarbonitrile) in solution in 100 ml ofanhydrous THF were degassed by flushing with dry argon. Copolymerizationof acrylonitrile with the styrene derivative was then carried out underargon at 60° C. during 48 hours. After cooling, the solution wasconcentrated, and the polymer was recovered by reprecipitation in ether.After filtering and drying, the lithium salt ofpoly-(acrylonitrile-co-5-(4styrenesulfonyl)-2,2-trifluoromethyl-1,3-dioxolane-4,6-dione)(PANS2MF) was obtained.

This polymer enables to introduce gelled polymer electrolytes with fixedanions. It constitutes the matrix enabling to obtain the gel and it hasthe properties of a polyelectrolyte. A gelled electrolyte made of 40% byweight of PANS2MF, 28% by weight of ethylene carbonate, 28% by weight ofpropylene carbonate and 4% by weight of silica particles (AEROSIL R 974commercially available from Degussa) was prepared. This gel has goodmechanical properties and a conductivity of 5.7×10⁻⁴ S.cm⁻¹ at 30° C.The cationic transport number of this electrolyte was estimated to be0.95.

An electrochemical generator was assembled by utilizing said gelledelectrolyte, a composite anode made of a carbon coke (80% by volume)mixed with the copolymer (PANS2MF) as binder (20% by volume), and acomposite cathode made of carbon black (6% by volume), LiCoO₂ (75% byvolume) and some copolymer (PANS2MF) as binder (20% by volume). Thisgenerator has enabled to effect 1,000 cycles of charge/discharge between3 and 4.2 V by maintaining a capacity higher than 80% of the capacityduring the first cycle, during a cycling 25° C. It has very goodperformances during calls for power because of the utilization of fixedanions. The utilization of fixed anions has also enabled to improve theevolution of the interface resistance.

EXAMPLE 16

According to a process similar to one used in Example 15, a copolymer ofacrylonitrile (97% molar) and a lithium salt of5-(4-styrenesulfonyl)-2,2-trifluoromethyl-1,3-dioxolane-4,6-dione acid(3% molar) was synthesized.

This copolymer, in the form of an alkali metal or ammonium salt, hasantistatic properties and may therefore advantageously replaceacrylonitrile homopolymers which are to this day largely utilized in theform of fiber for textile, but which has no antistatic properties.Moreover, spinning of this copolymer is easier than that of non-modifiedPAN.

The copolymer has very good interactions with cationic coloringmaterials such as methylene blue, which makes it a material of interestfor colored textile fibers. The stability of the color being clearlyimproved with respect to the known copolymer of acrylonitrile andmethallylsulfonate.

EXAMPLE 17

To 4.9 g of the sodium salt of Nickel (II) phthalocyaninetetrasulfonicacid (5 mmoles), commercially available from Aldrich) in 40 ml ofanhydrous dimethylformamide (DMF), there is added by portions 3.2 g of(chloromethylene)dimethylammonium chloride [(CH₃)₂N═CHCl]⁺,Cl⁻ ⁽25mmoles, commercially available from Aldrich). After 4 hours understirring, the reaction mixture was centrifuged, the floating liquid wasremoved and the decanted product was reclaimed in 40 ml of anhydrousDMH. There is then added 2 ml of pyridine and 7.81 g (20 mmoles) of thepotassium salt1-(2,2,3,3,3-pentafluoropropyl)-3-butyl-2-sulfonyl-barbituric acidobtained in Example 5. After 48 hours under stirring, the reactionmixture was stirred 24 hours with 2 g of potassium carbonate Li₂CO₃.After evaporation of DMF and drying, the following compound wasobtained:

which is soluble in most of the usual organic solvents(tetrahydrofurane, acetonitrile, dimethylfornamide, ethyl acetate,glymes, . . . ) and in polar polymers. It has an important absorption invisible range. In the form of tetrabutylammonium tetrasalt, it is alsosoluble in low polar solvents such as dichloromethane or methylenechloride as well as in low polar polymer matrices such as methylpolymethacrylate.

Grafting of1-(2,2,3,3,3-pentafluoropropyl)-3-butyl-2-sulfonyl-barbituric acid alsoenables to clearly decrease the aggregation of the molecules of thiscationic coloring materials between one another, which phenomenon ofaggregation brings about a widening of the optical absorption bandswhich is prejudicial to the preciseness of the systems utilizing itscoloring materials in particular optical disk for storing information.

EXAMPLE 18

To 3.2 g (25 mmoles) of 2-(3-thienyl)ethanol in 60 ml of anhydrousdimethylformamide, there is added 8.4 g (25 mmoles) of the potassiumsalt of 2-methyl-2-heptafluoropropyl-1,3-dioxolane-4,6-dione, obtainedin Example 8, 3.46 g of anhydrous potassium carbonate K₂CO₃ and 330 mg(1.25 mmoles) of a crown ether, 18-Crown-6 (acting as complexent of thepotassium cation). The reaction mixture was then stirred under argon at85° C. After 48 hours, the reaction mixture was filtered on a frittedglass of porosity N°3, and the solvent was evaporated under reducedpressure. After drying, the compound was recrystallized in 20 ml ofwater containing 1.86 g (25 mmoles) of anhydrous potassium chloride KCl.After filtering and drying, the following compound was recovered:

10 ml of a 5×10⁻² of said compound in acetonitrile were prepared and anelectropolymerization was carried out in the anodic compartment of anelectrochemical cell on a platinum electrode. A flexible conductor filmwas obtained:

in which the doping (oxidation) is ensured by exchange of cations andelectrons with the outside. The conductivity of this material is of theorder of 10 S.cm⁻¹ and it is stable at room temperature and in humidmedium. The electropolymerization carried out in the presence ofnon-substituted pyrrol or having oxyethylene chains in position N or 3gives polymers which are also stable and in which the change of colourmay be used to constitute electrochrome systems.

EXAMPLE 19

To 400 mg (1 mmole) of1-(2,2,3,3,4,4,4-heptafluorobutyl)-3-butyl-2-sulfonyl-barbituric acid,obtained in Example 5, in 5 ml of water under stirring, there are added2 drops of concentrated sulfuric acid. After 4 hours under stirring, 60mg of anhydrous lithium carbonate Li₂CO₃ were added, and after 15 min322 mg (1 mmole) of tetrabutylammonium (C₄H₉)₄NBr. By extraction withdichloromethane, the following compound was recovered:

This anionic absorbing coloring material in the visible range is solublein low polar solvents such as dichloromethane or methylene chloride aswell as in low polar polymer matrices such as methyl polymethacrylate.The low degree of aggregation of the molecules of this anionic colouringmaterial with one another prevents the phenomenon of widening of theoptical absorption bands of this colouring material.

EXAMPLE 20

In a three neck flask provided with a cooler, a mechanical stirrer and aneutral gas inlet (Argon), there is introduced 9.5 g of a copolymer ofdimethylsiloxane and (hydrogeno)(methyl)-siloxane (HMS 301 25% SiH,M_(w) 1900, commercially available from Gelest Inc., Tullytown, Pa.,USA) in solution in tetrahydrofurane. 14.03 g of the lithium salt of5-trifluoro-acetyl-3-allyl-1-butyl-barbituric, obtained in Example 1,and 70 mg of chloroplatinic acid H₂PtCl₆ were then added. The mixturewas heated to reflux during 4 hours. The polymer was then reprecipitatedin ether, redissolved in THF and again reprecipitated in ether. Thefollowing polymer was obtained:

which is soluble in most of the organic solvents, including atcontents >2% in oils or silicon materials, to which it gives antistaticproperties.

EXAMPLE 21

In a Parr chemical reactor, 12.9 g (50 mmoles) of the lithium salt of2,2-trifluoro-methyl-1,3-dioxolane-4,6-dione, obtained in Example 8, and176 mg of a crown ether, the 12-Crown-4 (acting as a complexent of thelithium cation) were solubilized in 60 ml of anhydrous acetonitrile.After closing the reactor, flushing with argon during 15 min was carriedout before isolating it. There are then introduced, 6.41 g (50 mmoles)of sulfur dioxide SO₂ (commercially available from Fluka), and, after 10min, 9.52 g (50 mmoles) of vinyltriethoxysilane (commercially availablefrom Fluka) in solution in 20 ml of anhydrous acetonitrile. After 6hours at room temperature, the reactor was heated to 40° C. and kept atthat temperature during 48 hours, and the solvent was evaporated. Afterdrying under vacuum, the following compound was obtained in quantitativeyield:

This salt may constitute organosilicon networks by a mechanism ofhydrolysis-polycondensation. It may also be used with glass basedmaterials (fiber,glazing, . . . ) in order to modify their surface andin particular to give them antistatic properties. A solution of thissalt with O-[2-(trimethoxysilyl)-ethyl]-O′-methylpolyethylene glycol ofmolecular weight 5,000 (commercially available from ShearwatersPolymers) (3:1 molar) was prepared in a water/methanol mixture. A glassplate cleaned with nitric acid and dried at 100° C. was then soaked inthe solution during a few minutes. After rinsing with methanol anddrying, a surface conductivity of 3×10⁻⁵ S(square) sufficient to giveantistatic and hydrophilic properties to the glass surface was measured.

EXAMPLE 22

5.97 g (10 mmoles) of the potassium salt of5-perfluorobutanesulfonyl-1,3-dibutyl-2-sulfonyl-barbituric acid,prepared according to Example 5, and 3.17 g (10 mmoles) ofdiphenyliodonium (C₆H₅)₂IClwere stirred together during 24 hours inwater. By extraction of the aqueous phase with dichloromethane, thefollowing compound was recovered:

This salt is particularly active as cationic polymerizationphotoinitiator, in particular for divinylethers such as triethyleneglycol divinylether (DVE-3). This initiator has a solubility and anactivity higher than that of the same sulfonium salt associated with PF₆⁻ or SbF₆ ⁻.

EXAMPLE 23

2.22 g (5 mmoles) of tetrakis(acetonitrile)palladium (II)tetra-fluoroborate (CH₃CN)₄Pd(BF₄)₂ (commercially available fromAldrich), in 30 ml of tetrahydrofurane, were treated with 5.97 g (10mmoles) of the potassium salt of5-perfluorobutanesulfonyl-1,3-dibutyl-2-sulfonyl-barbituric acidobtained in Example 2. After 24 hours under stirring, the reactionmixture was filtered to remove the precipitate of potassiumtetrafluoroborate KBF₄, and the solvent was evaporated. The followingcompound was obtained in quantitative yield:

This salt is a catalyst for the vinyl polymerization of norbomene evenin low polar solvents such as dichloromethane.

EXAMPLE 24

During a first step, ferrocene dilithium complexed withtetramethylethylenediamine (TMEDA) was prepared: In a glove box underargon, there is added 37 ml of freshly distilled TMEDA (247 mmoles) and40 ml of anhydrous hexane in a 1 l flask. There is then added drop wise154 ml of a 1.6 M solution of butyllithium in hexane (247 mmoles,commercially available from Aldrich). After 10 min, there is added dropwise 18.6 g of ferrocene (100 mmoles) in solution in 500 ml of anhydroushexane while keeping a strong stirring of the solution. After one night,orange crystals appeared in the solution, which were recovered byfiltering the solution on a fritted glass of porosity N°4. After dryingunder vacuum, there is obtained 28.4 g of 1,1′-dilithio-ferrocenee•2TMEDA (66% yield) which was preserved under argon.

8.61 g (20 mmoles) of this compound in 30 ml of anhydrous acetonitrilewere then treated with 4.89 g of 1,3-propane sultone (40 mmoles) in aglove box. After 24 hours at room temperature, 2 drops ofdimethylformnamide were added in the reaction mixture, and there isslowly added 5.08 g of oxalyl chloride ClCOCOCl (40 mmoles) in solutionin 15 ml of anhydrous dichloromethane. After 4 hours at roomtemperature, 5 ml of pyridine and 11.61 g (40 mmoles) of the potassiumsalt of 2,2-trifluoromethyl-1,3-dioxolane-4,6-dione prepared as inExample 8 were added. The reaction was continued during 24 hours, andthe reaction mixture was stirred 24 hours in the presence of 4 g oflithium carbonate Li₂CO₃. After filtering and evaporation of thesolvents, and drying, the following compound was recovered:

This salt is soluble in most of the usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in polar polymers.

It has a reversible redox couple. In polyethylene oxide, it was possibleto determine, on a platinum electrode of a diameter 125 μm, a reversiblepotential of 3.4 V towards a lithium electrode.

When dissolved in a liquid, gel or polymer electrolyte, it enables toprovide a protection in overcharge thereby acting as a redox shuttle. Italso enables to provide electrochrome systems with colouring materials.

EXAMPLE 25 Catalysis of an Aldol Condensation

The scandium salt of5-trfluoromethanesulfonyl-1,3-dubutyl-2-sulfonyl-barbituric acid wasobtained by treating the potassium salt, obtained in Example 2, with astoichiometric quantity of scandium tetrafluoroborate Sc(BF₄)₃ inacetonitrile. After filtering to eliminate the precipitate of potassiumtetrafluoroborate KBF₄ and evaporation of the solvent, the scandium saltof dibutylaminosulfonylmalononitrile (Sc(DBTFSB)₃) was recovered inquantitative yield.

The catalytic effect of this salt in an aldol condensation was evaluatedin the following manner. To a solution containing 507 mg (0.4 mmoles) ofthe scandium salt of5-trifluoromethylsulfonyl-1,3-dibutyl-2-sulfonyl-barbituric acid (10%molar) in 15 ml of dichloromethane, there is added a mixture of 1.05 g(6 mmoles) of 1-ene-2-methyl-1-silylacetal-1-methoxypropene(CH₃)₂C═C(OSiMe₃)OMe and 420 mg (4 mmoles) of benzaldehyde in 10 ml ofdichloromethane. After 16 hours under stirring at room temperature,water was added and the product was extracted with dichloromethane. Theorganic phase was washed with three fractions of 100 ml of water anddichloromethane was evaporated. The residue was then treated with atetrahydrofurane/HCl 1 M (20:1) mixture during 0.5 hours at 0° C. Afterdiluting with hexane, a saturated solution of sodium bicarbonate wasadded, and the product was extracted with dichloromethane. The organicphase was washed with a saturated solution of sodium chloride, and driedwith sodium sulfate. After evaporation of the solvents, the raw productwas chromatographed on silica gel.Methyl-3-hydroxy-2,2-dimethyl-phenylpropionate was obtained with a yieldof 91% in accordance with the results obtained with the ytterbiumtriflate salt of the prior art.

The same reaction was carried out with a decreased quantity of catalystby a factor near five, without decreasing the yield of the compoundmethyl-3-hydroxy-2,2-dimethyl-phenylprionate. This result is due to thebetter solubility in dichloromethane of the scandium salt of5-trifluoromethanesulfonyl-1,3-dibutyl-2-sulfonyl-barbituric acid, ascompared to the ytterbium triflate salt, used in the prior art.

EXAMPLE 26 Catalysis of an Addition of Michael

The catalytic effect of the scandium salt of5-trifluoromethanesulfonyl-1,3-dibutyl-2-sulfonyl-barbituric acid,obtained in Example 25, towards a Michael addition was evaluated in thefollowing manner. To a solution of 507 mg (0.4 mmoles) of the scandiumsalt of dibutylaminosulfonylmalononitrile (10% molar) in 10 ml ofdichloromethane, there is added a mixture of 840 mg (4 mmoles) ofchalcone and 1.05 g (6 mmoles) of1-ene-2-methyl-1-silylacetal-1-methoxypropene (CH₃)₂C═C(OSiMe₃)OMe in 10ml of dichloromethane. After 12 hours under stirring at roomtemperature, water is added and the product was extracted withdichloromethane. The organic phase was washed with three fractions of100 ml water, and dichloromethane was evaporated. The residue was thentreated with a tetrahydrofurane/HCl 1 M (20:1) mixture during 0.5 hoursat 0° C. After diluting with hexane, a saturated solution of sodiumbicarbonate was added, and the product was extracted withdichloromethane. The organic phase was washed with a saturated solutionof sodium chloride, and dried with sodium sulfate. After evaporation ofthe solvents, the raw product was chromatographed on a silica gel. The1,5-dicarbonylated compound was obtained with a yield of 85% inaccordance with the results obtained with the ytterbium triflate salt ofthe prior art.

The same reaction was carried out with a decreased quantity of catalystby a factor near five, without decreasing the yield in the1,5-dicarbonylated compound. This result is due to the better solubilityin the dichloromethane of the scandium salt of5-trifluoromethanesulfonyl-1,3-dibutyl-2-sulfonylbarbituric acid, ascompared to the ytterbium triflate salt.

EXAMPLE 27 Catalysis of a Friedel-Crafts Acylation Reaction

The catalytic effect of the scandium salt of5-trifluoromethanesulfonyl-1,3-dibutyl-2-sulfonyl-barbituric acid,obtained in Example 25, towards a Friedel-Crafts reaction of acylationwas evaluated in the following manner. In 40 ml of anhydrousnitromethane, there is added 887 mg (0.7 moles) of the scandium salt of5-trifluoromethylsulfonyl-1,3-dibutyl-2-sulfonyl-barbituric acid, and1.08 g (10 mmoles) of anisole and 2.04 g (20 mmoles) of aceticanhydride. After stirring during 10 min at 21° C., the reaction mixturewas diluted with 50 ml of ether and the reaction was inhibited with 100ml of a saturated solution of sodium bicarbonate NaHCO₃. Afterfiltration on Celite, the solution was extracted with three fractions of50 ml ether, then the collected ether phase was washed with a saturatedsolution of potassium chloride. After drying the ether phase withmagnesium sulfate and evaporation, 1.46 g of p-methoxyacetophenone (95%yield) were recovered with a purity characterized by a proton RMN higherthan 99%.

EXAMPLE 28

The catalytic effect of the scadium salt of5-trifluoromethanesulfonyl-1,3-dibutyl-2-sulfonyl-barbituric acid,obtained in Example 25, towards a Diels-Alder reaction, was evaluated bycarrying out the following reaction.

To a solution of 651 of freshly distilled cyclopentadiene (10 mmoles)and 701 mg of methylvinylketone in 10 ml of dichloromethane, there isadded 200 μmoles of the scandium salt of5-trifluoromethylsulfonyl-1,3-dibutyl-2-sulfonyl-barbituric acid. After24 hours at room temperature, the reaction mixture was filtered toremove the catalyst in suspension. There is obtained a reaction yield,determined by chromatography in gaseous phase, higher than 90%.

EXAMPLE 29

The lithium salt of5-trifluoromethyl-sulfonyl-1,3-dibutyl-2-sulfonyl-barbituric acid,obtained in Example 2, and the lithium salt of5-cyano-2,2-trifluoromethyl-1,3-dioxolane-4,6-dione acid, obtained inExample 8, were tested in electrochemical generators of lithium-polymertechnology.

For each salt, a battery was prepared by superposing the followinglayers:

a stainless steel current collector with a thickness of 2 mm;

a cathode consisting of a pastil of a film of composite material havinga thickness of 89 μm an consisting of vanadium dioxide (45% by volume),Shawinigan black (5% by volume) and polyethylene oxide of molecularweight M_(w)=3×10⁵ (50% by volume);

an electrolyte consisting of a pastil of a film of polyethylene oxide ofmolecular weight M_(w)=5×10⁶ containing one of the two lithium salts ata concentration O/Li=15/1;

an anode consisting of a sheet of metallic lithium having a thickness of50 μm;

a current collector similar to the above current collector.

The pastils constituting the electrodes and the electrolyte were cut ina glove box and piled in the order indicated above. The collectors werethen placed on both sides of the pile obtained.

The assembly was sealed in a button shaped battery housing which enablessimultaneously to protect the generator from the atmosphere and to exerta mechanical stress on the films. The battery was then placed in anenclosure under argon mounted in a drying oven at a temperature of 60°C. It was then cycled between 1.8 and 3.3 V at a rate of charge anddischarge C/10 (nominal capacity charge or discharge in 10 hours).

The curve of cycling obtained by utilizing the lithium salt of5-trifluoromethylsulfonyl-1,3-dibutyl-2-sulfonyl-barbituric acid isgiven in FIG. 1. In this figure, the utilization, U, expressed in % isgiven in ordinate, and the number of cycles, C, is given in abscissae.

Similar cycling result is obtained with the lithium salt of5-cyano-2,2-trifluoromethyl-1,3-dioxolane-4,6-dione acid.

What is claimed is:
 1. An ionically conductive material comprising anionic compound in solution in a solvent, said ionic compound comprisingat least one anionic part associated to at least one cationic part M insufficient number to ensure an electronic neutrality to the compound,characterized in that M is cation having a valency m selected from thegroup consisting of cations derived from ferrocene, titanocene,zirconocene, indenocenium cations, arene metallocenium cations, cationsof transition metals complexed with ligands of phosphine type optionallyhaving a chirality and organometallic cations having one or more alkylor aryl groups covalently fixed to an atom or a group of atoms, saidcations optionally being part of a polymer chain, and in that theanionic part is an aromatic heterocycle corresponding to formula

in which: Y₁, Y₂, and Y₃ represent independently from one another acarbonyl group, a sulfonyl group, a thiocarbonyl group, a thionyl group,a —C(═NCN)— group or a —C(═C(CN)₂)— group; Z represents anelectroattractor radical having a Hammett parameter at least equal tothat of a fluorine atom; each of the substituents R_(A) and R_(B)represent independently from one another a monovalent or divalentorganic radical, or is part of a polymer chain.
 2. An ionicallyconductive material according to claim 1, characterized in that thesubstituents R_(A) and R_(B) represent independently from one another:a) an alkyl, an alkenyl, an oxa-alkyl, an oxa-alkenyl, an aza-alkyl, anaza-alkenyl, a thia-alkyl, a thia-alkenyl, said radicals carrying atleast one aryl group; b) an aryl carrying at least one radical asdefined in a); c) an alicyclic radical or an aromatic radical optionallycarrying at least one lateral chain comprising a heteroatom oroptionally comprising at least one heteroatom in the cycle; d) a radicalas defined above in a), b) and c) and additionally carrying halogenatoms, in halogenated or perhalogenated form.
 3. An ionically conductivematerial according to claim 1, characterized in that Z is a R_(E)Y_(E)—radical or a R_(E)R_(G)PO— radical in which Y_(E) represents a carbonylgroup, a sulfonyl group or thionyl group, and R_(E) and R_(G) representindependently from one another a halogen or an organic radical.
 4. Anionically conductive material according to claim 3, characterized inthat R_(E) and R_(G) represent independently from one another an alkyl,alkenyl, oxaalkyl, oxaalkenyl, azaalkyl, azaalkenyl, thiaalkyl,thiaalkenyl, aryl, alkylaryl, alkenylaryl, arylalkyl, arylalkenylradical, an alicyclic radical or an aromatic radical optionally carryingat least one lateral chain comprising a heteroatom or optionallycomprising at least one hetero atom in the cycle, said R_(E) and R_(G)optionally being halogenated or perhalogenated.
 5. An ionicallyconductive material according to claim 3, characterized in that R_(E)and R_(G) are selected independently from alkyl or alkenyl radicalhaving from 1 to 12 carbon atoms and optionally comprising at least oneheteroatom O, N or S in the main chain or in a side chain, and carryinga hydroxy group, a carbonyl group, an amine group, a carboxyl group. 6.An ionically conductive material according to claim 3, characterized inthat R_(E) and R_(G) are selected independently from one another fromaryl, arylalkyl, alkylaryl or alkenylaryl radicals, in which thearomatic nuclei, optionally condensed, comprise heteroatoms such asnitrogen, oxygen, sulfur.
 7. An ionically conductive material accordingto claim 3, characterized in that R_(E) or R_(G) include at least oneethylenic unsaturation and/or a condensable group and/or a group whichis thermally, photochemnically or ionically dissociable.
 8. An ionicallyconductive material according to claim 3, characterized in that R_(E) orR_(G) includes a group capable of trapping free radicals.
 9. Anionically conductive material according to claim 3, characterized inthat R_(E) or R_(G) comprise a dissociating dipole or a redox couple ora complexing ligand.
 10. An ionically conductive material according toclaim 3, characterized in that R_(E)Y_(E)— or R_(E)R_(G)PO— is opticallyactive.
 11. Ionically conductive material according to claim 1,characterized in that the solvent is either an aprotic liquid solventselected from linear ethers and cyclic ethers, esters, nitrites, nitroderivatives, amides, sulfones, sulfolanes, sulfamides and partiallyhalogenated hydrocarbons, or a polar polymer, or a mixture thereof. 12.Ionically conductive material according to claim 1, characterized inthat the solvent consists essentially of an aprotic liquid solvent and apolar polymer solvent comprising units containing at least oneheteroatom selected from sulfur, oxygen, nitrogen and fluorine. 13.Ionically conductive material according to claim 12, characterized inthat the polar polymer mainly contains units derived from acrylonitrile,vinylidene fluoride, N-vinylpyrrolidone or methyl methacrylate.
 14. Anionically conductive material comprising an ionic compound in solutionin a solvent, said ionic compound comprising at least one anionic partassociated to at least one cationic part M in sufficient number toensure an electronic neutrality to the compound, characterized in that Mis a hydroxonium, a nitrosonium NO⁺, an ammonium —NH₄ ⁺, a metalliccation having a valency m, an organic cation having a valency m, or anorganometallic cation having a valency m, and in that the anionic partis an aromatic heterocycle corresponding to formula

in which: Y₁, Y₂, and Y₃ represent independently from one another acarbonyl group, a sulfonyl group, a thiocarbonyl group, a thionyl group,a —C(═NCN)— group or a —C(═C(CN)₂)— group; Z represents anelectroattractor radical having a Hammett parameter at least equal tothat of a fluorine atom; each of the substituents R_(A) and R_(B)represent independently from one another a monovalent or divalentorganic radical, or is part of a polymer chain, and characterized inthat the substituents R_(A) and R_(B) are selected independently fromone another from oxa-alkyl or oxa-alkenyl radicals having 1 to 10 carbonatoms.
 15. An ionically conductive material according to claim 14,characterized in that the organic cation is selected from a groupconsisting of cations R₃O⁺(oxonium), NR₄ ⁺(ammonium), RC(NHR₂)₂⁺(amidinium), C(NHR₂)₃ ⁺(guanidinium), C₅R₆N⁺(pyridiniurn), C₃R₅N₂⁺(imidazolium), C₃R₇N₂ ⁺(imidazolinium), C₂R₄N₃ ⁺(triazolium), SR₃⁺(sulfonium), PR₄ ⁺(phosphonium), IR₂ ⁺(iodonium), (C₆R₅)₃C⁺(carbonium),the radicals R independently representing an H or a radical selectedfrom the group consisting of: alkyl, alkenyl, oxa-alkyl, oxa-alkenyl,aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl, sila-alkyl,sila-alkenyl, aryl, arylalkyl, alkylaryl, alkenyl-aryl, dialkylamino anddialkylazo radicals; cyclic or heterocyclic radicals optionallycomprising at least one lateral chain comprising heteroatoms such asoxygen, nitrogen, sulfur; cyclic or heterocyclic radicals optionallycomprising heteroatoms in the aromatic nucleus; groups comprising aplurality of aromatic or heterocyclic nuclei, condensed ornon-condensed, optionally containing at least one nitrogen, oxygen,sulfur or phosphorus atom; with the proviso that a plurality of radicalsR may together form aliphatic or aromatic cycles optionally enclosingthe center carrying the cationic charge.
 16. An ionically conductivematerial according to claim 4, characterized in that the oxonium,ammonium, sulfonium, phosphonium, iodonium or carbonium cation is partof the radical Z.
 17. An ionically conductive material according toclaim 14, characterized in that the oxonium, ammonium, sulfonium,phosphonium, iodonium or carbonium cation is part of a recurring unit ofa polymer or is part of a polymer chain.
 18. An ionically conductivematerial according to claim 14, characterized in that the organic cationcomprises an imidazolium group, a triazolium group, a pyridinium group,a 4-dimethyl-amino-pyridinium group, said groups optionally carrying asubstituent on the carbon atoms of the cycle, or a group having a bond—N═N—, —N═N⁺, a sulfonium group, an iodonium group, or a substituted ornon-substituted arene-ferrocenium cation, optionally incorporated in apolymeric network, or a group2,2′[Azobis(2-2′-imidazolinio-2-yl)propane]²⁺ or2,2′-Azobis(2-amidinio-propane)²⁺.
 19. An ionically conductive materialaccording to claim 14, characterized in that the cation M is a metalliccation selected from the group consisting of cations of alkali metals,cations of alkali earth metals, cations of transition metals, cations oftrivalent metals, cations of rare earths and organometallic cations. 20.An ionically conductive material according to claim 14, characterized inthat Z is a R_(E)Y_(E)— radical or a R_(E)R_(G)PO— radical in whichY_(E) represents a carbonyl group, a sulfonyl group or thionyl group,and R_(E) and R_(G) represent independently from one another a halogenor an organic radical.
 21. An ionically conductive material according toclaim 20, characterized in that R_(E) and R_(G) represent independentlyfrom one another an alkyl, alkenyl, oxaalkyl, oxaalkenyl, azaalkyl,azaalkenyl, thiaalkyl, thiaalkenyl, aryl, alkylaryl, alkenylaryl,arylalkyl, arylalkenyl radical, an alicyclic radical or an aromaticradical optionally carrying at least one lateral chain comprising aheteroatom or optionally comprising at least one hetero atom in thecycle, said R_(E) and R_(G) optionally being halogenated orperhalogenated.
 22. An ionically conductive material according to claim20, characterized in that R_(E) and R_(G) are selected independentlyfrom alkyl or alkenyl radical having from 1 to 12 carbon atoms andoptionally comprising at least one heteroatom O, N or S in the mainchain or in a side chain, and carrying a hydroxy group, a carbonylgroup, an amine group, a carboxyl group.
 23. An ionically conductivematerial according to claim 20, characterized in that R_(E) and R_(G)are selected independently from one another from aryl, arylalkyl,alkylaryl or alkenylaryl radicals, in which the aromatic nuclei,optionally condensed, comprise heteroatoms such as nitrogen, oxygen,sulfur.
 24. An ionically conductive material according to claim 20,characterized in that R_(E) or R_(G) include at least one ethylenicunsaturation and/or a condensable group and/or a group whichisthermally, photochemically or ionically dissociable.
 25. An ionicallyconductive material according to claim 20, characterized in that R_(E)or R_(G) includes a group capable of trapping free radicals.
 26. Anionically conductive material according to claim 20, characterized inthat R_(E) or R_(G) comprise a dissociating dipole or a redox couple ora complexing ligand.
 27. An ionically conductive material according toclaims 20, characterized in that R_(E)Y_(E)— or R_(E)R_(G)PO— isoptically active.
 28. Ionically conductive material according to claim14, characterized in that the solvent is either an aprotic liquidsolvent selected from linear ethers and cyclic ethers, esters, nitrites,nitro derivatives, amides, sulfones, sulfolanes, sulfamides andpartially halogenated hydrocarbons, or a polar polymer, or a mixturethereof.
 29. Ionically conductive material according to claim 14,characterized in that the solvent consists essentially of an aproticliquid solvent and a polar polymer solvent comprising units containingat least one heteroatom selected from sulfur, oxygen, nitrogen andfluorine.
 30. Ionically conductive material according to claim 29,characterized in that the polar polymer mainly contains units derivedfrom acrylonitrile, vinylidene fluoride, N-vinylpyrrolidone or methylmethacrylate.
 31. An ionically conductive material comprising an ioniccompound in solution in a solvent, said ionic compound comprising atleast one anionic part associated to at least one cationic part M insufficient number to ensure an electronic neutrality to the compound,characterized in that M is a hydroxonium, a nitrosonium NO⁺, an ammonium—NH₄ ⁺, a metallic cation having a valency m, an organic cation having avalency m, or an organometallic cation having a valency m, and in thatthe anionic part is an aromatic heterocycle corresponding to formula

in which: Y₁, Y₂, and Y₃ represent independently from one another acarbonyl group, a sulfonyl group, a thiocarbonyl group, a thionyl group,a —C(═NCN)— group or a —C(═C(CN)₂)— group; Z represents anelectroattractor radical having a Hammett parameter at least equal tothat of a fluorine atom; each of the substituents R_(A) and R_(B)represent independently from one another a monovalent or divalentorganic radical, or is part of a polymer chain and characterized in thatZ is a radical R_(E)SO₂—.
 32. An ionically conductive material accordingto claim 31, characterized in that the substituents R_(A) and R_(B)represent independently from one another: a) an alkyl, an alkenyl, anoxa-alkyl, an oxa-alkenyl, an aza-alkyl, an aza-alkenyl, a thia-alkyl, athia-alkenyl, said radicals carrying at least one aryl group; b) an arylcarrying at least one radical as defined in a); c) an alicyclic radicalor an aromatic radical optionally carrying at least one lateral chaincomprising a heteroatom or optionally comprising at least one heteroatomin the cycle; d) a radical as defined above in a), b) and c) andadditionally carrying halogen atoms, in halogenated or perhalogenatedform.
 33. An ionically conductive material according to claim 31,characterized in that the organic cation is selected from a groupconsisting of cations R₃O⁺ (oxonium), NR₄ ⁺(ammonium), RC(NHR₂)₂⁺(amidinium), C(NHR₂)₃ ⁺(guanidinium), C₅R₆N⁺(pyridinium), C₃R₅N₂⁺(imidazolium), C₃R₇N₂ ⁺(imidazolinium), C₂R₄N₃ ⁺(triazolium), PR₄⁺(phosphonium), IR₂ ⁺(iodonium), (C₆R₅)₃C⁺(carbonium), the radicals Rindependently representing an H or a radical selected from the groupconsisting of: alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl,aza-alkenyl, thia-alkyl, thia-alkenyl, sila-alkyl, sila-alkenyl, aryl,arylalkyl, alkylaryl, alkenyl-aryl, dialkylamino and dialkylazoradicals; cyclic or heterocyclic radicals optionally comprising at leastone lateral chain comprising heteroatoms such as oxygen, nitrogen,sulfur; cyclic or heterocyclic radicals optionally comprisingheteroatoms in the aromatic nucleus; groups comprising a plurality ofaromatic or heterocyclic nuclei, condensed or non-condensed, optionallycontaining at least one nitrogen, oxygen, sulfur or phosphorus atom;with the proviso that a plurality of radicals R may together formaliphatic or aromatic cycles optionally enclosing the center carryingthe cationic charge.
 34. An ionically conductive material according toclaim 31, characterized in that the oxonium, ammonium, sulfonium,phosphonium, iodonium or carbonium cation is part of the radical Z. 35.An ionically conductive material according to claim 31, characterized inthat the oxonium, ammonium, sulfonium, phosphonium, iodonium orcarbonium cation is part of a recurring unit of a polymer or is part ofa polymer chain.
 36. An ionically conductive material according to claim31, characterized in that the organic cation comprises: an imidazoliumgroup, a triazolium group, a pyridinium group, a4-dimethyl-amino-pyridinium group, said groups optionally carrying asubstituent on the carbon atoms of the cycle, or a group having a bond—N═N—, —N═N⁺, a sulfonium group, an iodonium group, or a substituted ornon-substituted arene-ferrocenium cation, optionally incorporated in apolymeric network, or a group2,2′[Azobis(2-2′-imidazolinio-2-yl)propane]²⁺ or2,2′-Azobis(2-amidinio-propane)²⁺.
 37. An ionically conductive materialaccording to claim 31, characterized in that the cation M is a metalliccation selected from the group consisting of cations of alkali metals,cations of alkali earth metals, cations of transition metals, cations oftrivalent metals, cations of rare earths and organometallic cations. 38.An ionically conductive material according to claim 31, characterized inthat R_(E) represents an alkyl, alkenyl, oxaalkyl, oxaalkenyl, azaalkyl,azaalkenyl, thiaalkyl, thiaalkenyl, aryl, alkylaryl, alkenylaryl,arylalkyl, arylalkenyl radical, an alicyclic radical or an aromaticradical optionally carrying at least one lateral chain comprising aheteroatom or optionally comprising at least one hetero atom in thecycle, said R_(E) optionally being halogenated or perhalogenated.
 39. Anionically conductive material according to claim 31, characterized inthat R_(E) is selected from alkyl or alkenyl radical having from 1 to 12carbon atoms and optionally comprising at least one heteroatom O, N or Sin the main chain or in a side chain, and carrying a hydroxy group, acarbonyl group, an amine group, a carboxyl group.
 40. An ionicallyconductive material according to claim 31, characterized in that R_(E)is selected from aryl, arylalkyl, alkylaryl or alkenylaryl radicals, inwhich the aromatic nuclei, optionally condensed, comprise heteroatomssuch as nitrogen, oxygen, sulfur.
 41. An ionically conductive materialaccording to claim 31, characterized in that R_(E) includes at least oneethylenic unsaturation and/or a condensable group and/or a group whichis thermally, photochemically or ionically dissociable, and or a groupcapable of trapping free radicals.
 42. An ionically conductive materialaccording to claim 31, characterized in that R_(E) comprises adissociating dipole or a redox couple or a complexing ligand.
 43. Anionically conductive material according to claim 31, characterized inthat R_(E)SO₂— is optically active.
 44. Ionically conductive materialaccording to claim 31, characterized in that the solvent is either anaprotic liquid solvent selected from linear ethers and cyclic ethers,esters, nitriles, nitro derivatives, amides, sulfones, sulfolanes,sulfamides and partially halogenated hydrocarbons, or a polar polymer,or a mixture thereof.
 45. Ionically conductive material according toclaim 31, characterized in that the solvent consists essentially of anaprotic liquid solvent and a polar polymer solvent comprising unitscontaining at least one heteroatom selected from sulfur, oxygen,nitrogen and fluorine.
 46. Ionically conductive material according toclaim 45, characterized in that the polar polymer mainly contains unitsderived from acrylonitrile, vinylidene fluoride, N-vinylpyrrolidone ormethyl methacrylate.
 47. An ionically conductive material comprising anionic compound in solution in a solvent, said ionic compound comprisingat least one anionic part associated to at least one cationic part M insufficient number to ensure an electronic neutrality to the compound,characterized in that M is a hydroxonium, a nitrosonium NO⁺, an ammonium—NH₄ ⁺, a metallic cation having a valency m, an organic cation having avalency m, or an organometallic cation having a valency m, and in thatthe anionic part is an aromatic heterocycle corresponding to formula

in which: Y₁, Y₂, and Y₃ represent independently from one another acarbonyl group, a sulfonyl group, a thiocarbonyl group, a thionyl group,a —C(═NCN)— group or a —C(═C(CN)₂)— group; Z represents anelectroattractor radical having a Hammett parameter at least equal tothat of a fluorine atom; each of the substituents R_(A) and R_(B)represent independently from one another a monovalent or divalentorganic radical, or is part of a polymer chain, and characterized inthat Z is a R_(E)Y_(E)— radical or a R_(E)R_(G)PO— radical in which:Y_(E) represents a carbonyl group, a sulfonyl group or thionyl group,and R_(E) and R^(G) represent independently from one another a radicalhaving an iodonium, sulfonium, oxonium, ammonium, amidinium,guanidinium, pyridinium, imidazolium, triazolium, phosphonium orcarbonium group, said ionic group behaving totally or partially ascation M, or R_(E) or R_(G) represents a mesomorphous group or achromophore group or a self-doped electronically conductive polymer or ahydrolyzable alkoxysilane, or R_(E)Y_(E)— represents an amino acid, oran optically or biologically active polypeptide, or R_(E) or R_(G) ispart of a poly(oxyalkylene) radical or of a polystyrene radical.
 48. Anionically conductive material according to claim 47, characterized inthat the substituents R_(A) and R_(B) represent independently from oneanother: a) an alkyl, an alkenyl, an oxa-alkyl, an oxa-alkenyl, anaza-alkyl, an aza-alkenyl, a thia-alkyl, a thia-alkenyl, said radicalscarrying at least one aryl group; b) an aryl carrying at least oneradical as defined in a); c) an alicyclic radical or an aromatic radicaloptionally carrying at least one lateral chain comprising a heteroatomor optionally comprising at least one heteroatom in the cycle; d) aradical as defined above in a), b) and c) and additionally carryinghalogen atoms, in halogenated or perhalogenated form.
 49. An ionicallyconductive material according to claim 47, characterized in that theorganic cation is selected from a group consisting of cations R₃O⁺(oxonium), NR₄ ⁺(ammonium), RC(NHR₂)₂ ⁺(amidinium), C(NHR₂)₃⁺(guanidinium), C₅R₆N⁺(pyridinium), C₃R₅N₂ ⁺(imidazolium), C₃R₇N₂⁺(imidazolinium), C₂R₄N₃ ⁺(triazolium), SR₃ ⁺(sulfonium), PR₄⁺(phosphonium), IR₂ ⁺(iodonium), (C₆R₅)₃C⁺(carbonium), the radicals Rindependently representing an H or a radical selected from the groupconsisting of: alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl,aza-alkenyl, thia-alkyl, thia-alkenyl, sila-alkyl, sila-alkenyl, aryl,arylalkyl, alkylaryl, alkenyl-aryl, dialkylamino and dialkylazoradicals; cyclic or heterocyclic radicals optionally comprising at leastone lateral chain comprising heteroatoms such as oxygen, nitrogen,sulfur; cyclic or heterocyclic radicals optionally comprisingheteroatoms in the aromatic nucleus; groups comprising a plurality ofaromatic or heterocyclic nuclei, condensed or non-condensed, optionallycontaining at least one nitrogen, oxygen, sulfur or phosphorus atom;with the proviso that a plurality of radicals R may together formaliphatic or aromatic cycles optionally enclosing the center carryingthe cationic charge.
 50. An ionically conductive material according toclaim 47, characterized in that the oxonium, ammonium, sulfonium,phosphonium, iodonium or carbonium cation is part of the radical Z. 51.An ionically conductive material according to claim 47, characterized inthat the oxonium, ammonium, sulfonium, phosphonium, iodonium orcarbonium cation is part of a recurring unit of a polymer or is part ofa polymer chain.
 52. An ionically conductive material according to claim47, characterized in that the organic cation comprises: an imidazoliumgroup, a triazolium group, a pyridinium group, a4-dimethyl-amino-pyridinium group, said groups optionally carrying asubstituent on the carbon atoms of the cycle, or a group having a bond—N═N—, —N═N⁺, a sulfonium group, an iodonium group, or a substituted ornon-substituted arene-ferrocenium cation, optionally incorporated in apolymeric network, or a group2,2′[Azobis(2-2′-imidazolinio-2-yl)propane]²⁺ or2,2′-Azobis(2-amidinio-propane)²⁺.
 53. An ionically conductive materialaccording to claim 47, characterized in that the cation M is a metalliccation selected from the group consisting of cations of alkali metals,cations of alkali earth metals, cations of transition metals, cations oftrivalent metals, cations of rare earths and organometallic cations. 54.Ionically conductive material according to claim 47, characterized inthat the solvent is either an aprotic liquid solvent selected fromlinear ethers and cyclic ethers, esters, nitrites, nitro derivatives,amides, sulfones, sulfolanes, sulfamides and partially halogenatedhydrocarbons, or a polar polymer, or a mixture thereof.
 55. Ionicallyconductive material according to claim 47, characterized in that thesolvent consists essentially of an aprotic liquid solvent and a polarpolymer solvent comprising units containing at least one heteroatomselected from sulfur, oxygen, nitrogen and fluorine.
 56. Ionicallyconductive material according to claim 55, characterized in that thepolar polymer mainly contains units derived from acrylonitrile,vinylidene fluoride, N-vinylpyrrolidone or methyl methacrylate.
 57. Anionically conductive material comprising an ionic compound in solutionin a solvent, said ionic compound comprising at least one anionic partassociated to at least one cationic part M in sufficient number toensure an electronic neutrality to the compound, characterized in that Mis a hydroxonium, a nitrosonium NO⁺, an ammonium —NH₄ ⁺, a metalliccation having a valency m, an organic cation having a valency m, or anorganometallic cation having a valency m, and in that the anionic partis an aromatic heterocycle corresponding to formula

in which: Y₁, Y₂, and Y₃ represent independently from one another acarbonyl group, a sulfonyl group, a thiocarbonyl group, a thionyl group,a —C(═NCN)— group or a —C(═C(CN)₂)— group; Z represents anelectroattractor radical having a Hammett parameter at least equal tothat of a fluorine atom; each of the substituents R_(A) and R_(B)represent independently from one another a monovalent or divalentorganic radical, or is part of a polymer chain, characterized in that: Zis selected from a group consisting of —F, —Cl, —Br, —CN, —NO₂, —SCN and—N₃, or Z is selected from a group consisting of —C_(n)F₂₊₁,—O—C_(n)F_(2n+1), —S—C_(n)F_(2n+1), —CH₂—C_(n)F₂₊₁, —OCF═CF₂ or—SCF═CF₂, 1≦n≦8, —OC₂F₄H and —SC₂F₄H, or Z comprises a heterocyclederived from fluorinated or non-fluorinated pyridine, pyrazine,pyrimidine, oxadiazole or thiadiazole, or Z is a bivalent radicalcomprising at least one —SO₂— group, one —CO— group, a perfluoroalkylenehaving 2 to 8 carbon atoms, a phenylene group optionally substitutedwith heteroatoms, a —(W═W)_(n)— group or a cationic group—(W═W)_(n)—W⁺—, in which W represents a nitrogen atom or a —C(R)— group,R representing a hydrogen atom or an organic radical having 1 to 8carbon atoms, or two radicals R carried by adjacent carbon atoms forminga cycle, and 0≦n≦5, or Z is a radical having a valency v at least equalto 2 and connecting v ionic groups


58. An ionically conductive material according to claim 57,characterized in that the substituents R_(A) and R_(B) representindependently from one another: a) an alkyl, an alkenyl, an oxa-alkyl,an oxa-alkenyl, an aza-alkyl, an aza-alkenyl, a thia-alkyl, athia-alkenyl, said radicals carrying at least one aryl group; b) an arylcarrying at least one radical as defined in a); c) an alicyclic radicalor an aromatic radical optionally carrying at least one lateral chaincomprising a heteroatom or optionally comprising at least one heteroatomin the cycle; d) a radical as defined above in a), b) and c) andadditionally carrying halogen atoms, in halogenated or perhalogenatedform.
 59. An ionically conductive material according to claim 57,characterized in that the organic cation is selected from a groupconsisting of cations R₃O⁺(oxonium), NR₄ ⁺(ammonium), RC(NHR₂)₂⁺(amidinium), C(NHR₂)₃ ⁺(guanidinium), C₅R₆N⁺(pyridinium), C₃R₅N₂⁺(imidazolium), C₃R₇N₂ ⁺(imidazolinium), C₂R₄N₃ ⁺(triazolium), SR₃⁺(sulfonium), PR₄ ⁺(phosphonium), IR₂ ⁺(iodonium), (C₆R₅)₃C⁺(carbonium),the radicals R independently representing an H or a radical selectedfrom the group consisting of: alkyl, alkenyl, oxa-alkyl, oxa-alkenyl,aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl, sila-alkyl,sila-alkenyl, aryl, arylalkyl, alkylaryl, alkenyl-aryl, dialkylamino anddialkylazo radicals; cyclic or heterocyclic radicals optionallycomprising at least one lateral chain comprising heteroatoms such asoxygen, nitrogen, sulfur; cyclic or heterocyclic radicals optionallycomprising heteroatoms in the aromatic nucleus; groups comprising aplurality of aromatic or heterocyclic nuclei, condensed ornon-condensed, optionally containing at least one nitrogen, oxygen,sulfur or phosphorus atom; with the proviso that a plurality of radicalsR may together form aliphatic or aromatic cycles optionally enclosingthe center carrying the cationic charge.
 60. An ionically conductivematerial according to claim 57, characterized in that the oxonium,ammonium, sulfonjium, phosphonium, iodonium or carbonium cation is partof the radical Z.
 61. An ionically conductive material according toclaim 57, characterized in that the oxonium, ammonium, sulfonium,phosphonium, iodonium or carbonium cation is part of a recurring unit ofa polymer or is part of a polymer chain.
 62. An ionically conductivematerial according to claim 57, characterized in that the organic cationcomprises: an imidazolium group, a triazolium group, a pyridinium group,a 4-dimethyl-amino-pyridinium group, said groups optionally carrying asubstituent on the carbon atoms of the cycle, or a group having a bond—N═N—, —N═N⁺, a sulfonium group, an iodonium group, or a substituted ornon-substituted arene-ferrocenium cation, optionally incorporated in apolymeric network, or a group2,2′[Azobis(2-2′-imidazolinio-2-yl)propane]²⁺ or2,2′-Azobis(2-amidinio-propane)²⁺.
 63. An ionically conductive materialaccording to claim 57, characterized in that the cation M is a metalliccation selected from the group consisting of cations of alkali metals,cations of alkali earth metals, cations of transition metals, cations oftrivalent metals, cations of rare earths and organometallic cations. 64.Ionically conductive material according to claim 57, characterized inthat the solvent is either an aprotic liquid solvent selected fromlinear ethers and cyclic ethers, esters, nitriles, nitro derivatives,amides, sulfones, sulfolanes, sulfamides and partially halogenatedhydrocarbons, or a polar polymer, or a mixture thereof.
 65. Ionicallyconductive material according to claim 57, characterized in that thesolvent consists essentially of an aprotic liquid solvent and a polarpolymer solvent comprising units containing at least one heteroatomselected from sulfur, oxygen, nitrogen and fluorine.
 66. Ionicallyconductive material according to claim 65, characterized in that thepolar polymer mainly contains units derived from acrylonitrile,vinylidene fluoride, N-vinylpyrrolidone or methyl methacrylate.
 67. Anionically conductive material comprising an ionic compound in solutionin a solvent, said ionic compound comprising at least one anionic partassociated to at least one cationic part M in sufficient number toensure an electronic neutrality to the compound, characterized in that Mis a hydroxonium, a nitrosoniurn NO⁺, an ammonium —NH₄ ⁺, a metalliccation having a valency m, an organic cation having a valency m, or anorganometallic cation having a valency m, and in that the anionic partis an aromatic heterocycle corresponding to formula

in which: Y₁, Y₂, and Y₃ represent independently from one another acarbonyl group, a sulfonyl group, a thiocarbonyl group, a thionyl group,a —C(═NCN)— group or a —C(═C(CN)₂)— group; Z represents anelectroattractor radical having a Hammett parameter at least equal tothat of a fluorine atom; each of the substituents R_(A) and R_(B)represent independently from one another a monovalent or divalentorganic radical, or is part of a polymer chain and characterized in thatZ is part of a recurring unit of a polymer chain.
 68. An ionicallyconductive material comprising an ionic compound in solution in asolvent, said ionic compound comprising at least one anionic partassociated to at least one cationic part M in sufficient number toensure an electronic neutrality to the compound, characterized in that Mis a hydroxonium, a nitrosonium NO⁺, an ammonium —NH₄ ⁺, a metalliccation having a valency m, an organic cation having a valency m, or anorganometallic cation having a valency m, and in that the anionic partis an aromatic heterocycle corresponding to formula

in which: Y₁, Y₂, and Y₃ represent independently from one another acarbonyl group, a sulfonyl group, a thiocarbonyl group, a thionyl group,a —C(═NCN)— group or a —C(═C(CN)₂)— group; Z represents anelectroattractor radical having a Hammett parameter at least equal tothat of a fluorine atom; each of the substituents R_(A) and R_(B)represent independently from one another a monovalent or divalentorganic radical, or is part of a polymer chain, and characterized inthat it additionally contains at least a second salt and/or a mineral ororganic charge in the form of powder or fibers.
 69. An ionicallyconductive material comprising an ionic compound in solution in asolvent, said ionic compound comprising at least one anionic partassociated to at least one cationic part M in sufficient number toensure an electronic neutrality to the compound, characterized in that Mis a hydroxonium, a nitrosonium NO⁺, an ammonium —NH₄ ⁺, a metalliccation having a valency m, an organic cation having a valency m, or anorganometallic cation having a valency m, and in that the anionic partis an aromatic heterocycle corresponding to formula

in which: Y₁, Y₂, and Y₃ represent independently from one another acarbonyl group, a sulfonyl group, a thiocarbonyl group, a thionyl group,a —C(═NCN)— group or a —C(═C(CN)₂)— group; Z represents anelectroattractor radical having a Hammett parameter at least equal tothat of a fluorine atom; each of the substituents R_(A) and R_(B)represent independently from one another a monovalent or divalentorganic radical, or is part of a polymer chain, characterized in thatthe solvent is a solvating polymer, cross-linked or non-cross-linked,which may carry grafted ionic groups.
 70. Ionically conductive materialaccording to claim 69, characterized in that the solvating polymer isselected from polyethers of linear structure, comb or blocks, which mayform a network based on poly(ethylene oxide), copolymers containingethylene oxide or allylglycidylether units, polyphosphazenes,cross-linked networks based on polyethylene glycol cross-linked withisocyanates, networks obtained by polycondensation and carrying groupswhich enable the incorporation of cross-linkable groups and blockcopolymers in which certain blocks carry functions with redoxproperties.
 71. Electrochemical generator comprising a negativeelectrode and a positive electrode separated by an electrolyte,characterized in that the electrolyte is an ionically conductivematerial comprising an ionic compound in solution in a solvent, saidionic compound comprising at least one anionic part associated to atleast one cationic part M in sufficient number to ensure an electronicneutrality to the compound, characterized in that M is a hydroxonium, anitrosonium NO⁺, an ammonium —NH₄ ⁺, a metallic cation having a valencym, an organic cation having a valency m, or an organometallic cationhaving a valency m, and in that the anionic part is an aromaticheterocycle corresponding to formula

in which: Y₁, Y₂, and Y₃ represent independently from one another acarbonyl group, a sulfonyl group, a thiocarbonyl group, a thionyl group,a —C(═NCN)— group or a —C(═C(CN)₂)— group; Z represents anelectroattractor radical having a Hammett parameter at least equal tothat of a fluorine atom; each of the substituents R_(A) and R_(B)represent independently from one another a monovalent or divalentorganic radical, or is part of a polymer chain.
 72. Generator accordingto claim 71, characterized in that the negative electrode consists ofmetallic lithium, or an alloy thereof, optionally in the form ofnanometric dispersion in lithium oxide, or a double nitride of lithiumand a transition metal, or an oxide with low potential having thegeneral formula Li_(1+y+x/3)Ti_(2−x/3)O₄(0≦x≦1, 0≦y≦1), or carbon andcarbonated products produced by pyrolysis of organic material. 73.Generator according to claim 71, characterized in that the positiveelectrode is selected from vanadium oxides VO_(x)(2≦x≦2,5), LiV₃O₈,Li_(y)Ni_(1−x)Co_(x)O₂, (0≦x≦1; 0≦y≦1), spinels if manganeseLi_(y)Mn_(1−x)M_(x)O₂(M=Cr, Al, V, Ni, 0≦x≦0,5; 0≦y≦2), organicpolydisulfides, FeS, FeS₂, iron sulfate Fe₂(SO₄)₃, phosphates andphosphosilicates of iron and lithium olivine structure, or substitutedproducts wherein iron is replaced by manganese, used alone or inmixtures.
 74. Generator according to claim 71, characterized in that thecollector of the cathode is made of aluminum.
 75. Generator according toclaim 71, characterized in that the cation M is a metallic cationselected from the group consisting of cations of alkali metals, cationsof alkali earth metals, cations of transition metals, cations oftrivalent metals, cations of rare earths and organometallic cations. 76.A supercapacitor utilizing at least one carbon electrode with highspecific surface, or at least one electrode containing a redox polymer,in which the electrolyte is an ionically conductive material comprisingan ionic compound in solution in a solvent, said ionic compoundcomprising at least one anionic part associated to at least one cationicpart M in sufficient number to ensure an electronic neutrality to thecompound, characterized in that M is a hydroxonium, a nitrosonium NO⁺,an ammonium —NH₄ ⁺, a metallic cation having a valency m, an organiccation having a valency m, or an organometallic cation having a valencym, and in that the anionic part is an aromatic heterocycle correspondingto formula

in which: Y₁, Y₂, and Y₃ represent independently from one another acarbonyl group, a sulfonyl group, a thiocarbonyl group, a thionyl group,a —C(═NCN)— group or a —C(═C(CN)₂)— group; Z represents anelectroattractor radical having a Hammett parameter at least equal tothat of a fluorine atom; each of the substituents R_(A) and R_(B)represent independently from one another a monovalent or divalentorganic radical, or is part of a polymer chain.
 77. A process of usingan ionically conductive material comprising an ionic compound insolution in a solvent, said ionic compound comprising at least oneanionic part associated to at least one cationic part M in sufficientnumber to ensure an electronic neutrality to the compound, characterizedin that M is a hydroxonium, a nitrosonium NO⁺, an ammonium —NH₄ ⁺, ametallic cation having a valency m, an organic cation having a valencym, or an organometallic cation having a valency m, and in that theanionic part is an aromatic heterocycle corresponding to formula

in which: Y₁, and Y₃ represent independently from one another a carbonylgroup, a sulfonyl group, a thiocarbonyl group, a thionyl group, a—C(═NCN)— group or a —C(═C(CN)₂)— group; Z represents anelectroattractor radical having a Hammett parameter at least equal tothat of a fluorine atom; each of the substituents R_(A) and R_(B)represent independently from one another a monovalent or divalentorganic radical, or is part of a polymer chain for doping p or n apolymer with electronic conduction, said process comprising contacting ap or n polymer with said material.
 78. Electrochrome device, in whichthe electrolyte is an ionically conductive material comprising an ioniccompound in solution in a solvent, said ionic compound comprising atleast one anionic part associated to at least one cationic part M insufficient number to ensure an electronic neutrality to the compound,characterized in that M is a hydroxonium, a nitrosonium NO⁺, an ammonium—NH₄ ⁺, a metallic cation having a valency m, an organic cation having avalency m, or an organometallic cation having a valency m, and in thatthe anionic part is an aromatic heterocycle corresponding to formula

in which: Y₁, Y₂, and Y₃ represent independently from one another acarbonyl group, a sulfonyl group, a thiocarbonyl group, a thionyl group,a —C(═NCN)— group or a —C(═C(CN)₂)— group; Z represents anelectroattractor radical having a Hammett parameter at least equal tothat of a fluorine atom; each of the substituents R_(A) and R_(B)represent independently from one another a monovalent or divalentorganic radical, or is part of a polymer chain.
 79. Electronicallyconductive material, characterized in that it contains an ionicallyconductive material comprising an ionic compound in solution in asolvent, said ionic compound comprising at least one anionic partassociated to at least one cationic part M in sufficient number toensure an electronic neutrality to the compound, characterized in that Mis a hydroxonium, a nitrosonium NO⁺, an ammonium —NH₄ ⁺, a metalliccation having a valency m, an organic cation having a valency m, or anorganometallic cation having a valency m, and in that the anionic partis an aromatic heterocycle corresponding to formula

in which: Y₁, Y₂, and Y₃ represent independently from one another acarbonyl group, a sulfonyl group, a thiocarbonyl group, a thionyl group,a —C(═NCN)— group or a —C(═C(CN)₂)— group; Z represents anelectroattractor radical having a Hammett parameter at least equal tothat of a fluorine atom; each of the substituents R_(A) and R_(B)represent independently from one another a monovalent or divalentorganic radical, or is part of a polymer chain, and characterized inthat, in the ionic compound, at least one of the substituents of theanionic aromatic heterocycle contains an alkyl chain having 6 to 20carbon atoms.
 80. Electronically conductive material characterized inthat it contains an ionically conductive material comprising an ioniccompound in solution in a solvent, said ionic compound comprising atleast one anionic part associated to at least one cationic part M insufficient number to ensure an electronic neutrality to the compound,characterized in that M is a hydroxonium, a nitrosonium NO⁺, an ammonium—NH₄ ⁺, a metallic cation having a valency m, an organic cation having avalency m, or an organometallic cation having a valency m, and in thatthe anionic part is an aromatic heterocycle corresponding to formula

in which: Y₁, Y₂, and Y₃ represent independently from one another acarbonyl group, a sulfonyl group, a thiocarbonyl group, a thionyl group,a —C(═NCN)— group or a —C(═C(CN)₂)— group; Z represents anelectroattractor radical having a Hammett parameter at least equal tothat of a fluorine atom; each of the substituents R_(A) and R_(B)represent independently from one another a monovalent or divalentorganic radical, or is part of a polymer chain, and, characterized inthat the cationic part of the ionic compound is a polycation consistingof a doped conjugated polymer “p”.
 81. A process of using a material ina catalytic reaction, said reaction selected from the group consistingof Friedel-Crafts reactions, Diels and Alder reactions, aldolizationreactions, additions of Michael, reactions of allylation, reactions ofpinacolic coupling, reactions of allylation, reactions of cyclicopenings of oxetane, reactions of metathesis of alkenes, polymerizationsof Ziegler-Natta type, polymerizations of metathesis type by cycleopening and polymerizations of the metathesis type of acyclic dienes,said process comprising adding to a reaction mixture, a materialcomprising an ionic compound in solution in a solvent, said ioniccompound comprising at least one anionic part associated to at least onecationic part M in sufficient number to ensure an electronic neutralityto the compound, characterized in that M is a hydroxonium, a nitrosoniumNO⁺, an ammonium —NH₄ ⁺, a metallic cation having a valency m, anorganic cation having a valency m, or an organometallic cation having avalency m, and in that the anionic part is an aromatic heterocyclecorresponding to formula

in which: Y₁, Y₂, and Y₃ represent independently from one another acarbonyl group, a sulfonyl group, a thiocarbonyl group, a thionyl group,a —C(═NCN)— group or a —C(═C(CN)₂)— group; Z represents anelectroattractor radical having a Hammett parameter at least equal tothat of a fluorine atom; each of the substituents R_(A) and R_(B)represent independently from one another a monovalent or divalentorganic radical, or is part of a polymer chain.
 82. Process formodifying the solubility properties of a polymer having groups sensitivetowards acids, characterized in that it consists in subjecting saidpolymer to actinic radiation or β radiation, in the presence of amaterial comprising an ionic compound in solution in a solvent, saidionic compound comprising at least one anionic part associated to atleast one cationic part M in sufficient number to ensure an electronicneutrality to the compound, characterized in that M is a hydroxonium, anitrosonium NO⁺, an ammonium —NH₄ ⁺, a metallic cation having a valencym, an organic cation having a valency m, or an organometallic cationhaving a valency m, and in that the anionic part is an aromaticheterocycle corresponding to formula

in which: Y₁, Y₂, and Y₃ represent independently from one another acarbonyl group, a sulfonyl group, a thiocarbonyl group, a thionyl group,a —C(═NCN)— group or a —C(═C(CN)D— group; Z represents anelectroattractor radical having a Hammett parameter at least equal tothat of a fluorine atom; each of the substituents R_(A) and R_(B)represent independently from one another a monovalent or divalentorganic radical, or is part of a polymer chain.
 83. A process accordingto claim 82, characterized in that the polymer contains ester units orarylether units derived from tertiary alcohol.
 84. A process accordingto claim 83, characterized in that the polymer is selected from thegroup consisting of tertio-butyl polyacrylates, tertiobutyl ortertioamyl polyitaconates, poly(tertiobutoxycarbonyloxystyrene),poly(tertiobutoxystyrene).
 85. A process according to claim 82,characterized in that it is used for the chemical amplification ofphotoresists.